Ring-opening polymerizations using a flow reactor

ABSTRACT

Techniques regarding the synthesis of polyesters and/or polycarbonates through one or more ring-opening polymerizations conducted within a flow reactor and facilitated by a urea anion catalyst and/or a thiourea catalyst are provided. For example, one or more embodiments can comprise a method, which can comprise polymerizing, via a ring-opening polymerization within a flow reactor, a cyclic monomer in the presence an organocatalyst comprising a urea anion.

BACKGROUND

The subject disclosure relates to the use of a flow reactor tofacilitate one or more ring-opening polymerizations, and morespecifically, to using one or more flow reactors to facilitate one ormore ring-opening polymerizations comprising a urea and/or thioureaanion catalyst.

The United States federal government publishes regulations (e.g., GoodManufacturing Practices (GMP)) to ensure the quality of pharmaceuticalcompounds, medical devices, and/or food. These regulations can regardthe manufacturing, processing, packaging, and/or formulation of variousproducts. Moreover, these regulations address issues of production,starting materials, sanitation, cleanliness of equipment, and/ormonitoring through requisite tests. To meet these regulations,traditional industrialization techniques in the chemical industry haveincluded batch processing, in which a series of operations are carriedout over a period of time on a separate, identifiable item or parcel ofmaterial. Numerous chemical process industries retain batch processingas their primary method of manufacture. For example, productstraditionally manufactured by batch processing can includepharmaceuticals, agrochemicals, dyestuffs, food additives, vitamins,and/or the like. For instance, numerous polymers, such as polyestersand/or polycarbonates, have been traditionally manufactured using batchprocessing.

However, batch processing can be time-consuming, require the design ofmanufacturing stages that can be difficult to reproduce, can necessitateadverse safety conditions (e.g., due to the transportation of chemicalsand/or storage of volatile chemicals), can require a large labor force,and/or can be difficult to automate.

SUMMARY

The following presents a summary to provide a basic understanding of oneor more embodiments of the invention. This summary is not intended toidentify key or critical elements, or delineate any scope of theparticular embodiments or any scope of the claims. Its sole purpose isto present concepts in a simplified form as a prelude to the moredetailed description that is presented later. In one or more embodimentsdescribed herein, systems, apparatuses, and/or methods that can regardone or more ring-opening polymerizations within one or more flowreactors are described.

According to an embodiment, a method is provided. The method cancomprise polymerizing, via a ring-opening polymerization within a flowreactor, a cyclic monomer in the presence an organocatalyst comprising aurea anion. An advantage of such a method can include the implementationof continuous processing to increase chemical reaction rates, ascompared to traditional techniques. In some examples, the method cancomprise reacting, via a second ring-opening polymerization within theflow reactor, an intermediate polymer with a second cyclic monomer inthe presence of a chemical compound to form a block copolymer. Theintermediate polymer can be formed from the polymerizing the cyclicmonomer. Also, the chemical compound can comprise a functional groupselected from a group consisting of a urea group and a thiourea group.An advantage of such a method can include the implementation ofcontinuous processing to manufacture one or more copolymers (e.g., blockcopolymers).

According to another embodiment, a method is provided. The method cancomprise polymerizing, via a ring-opening polymerization within a flowreactor, a cyclic monomer in the presence of an organocatalystcomprising a thiourea anion. An advantage of such a method can includethe implementation of continuous processing to achieve manufacturingtechniques that are highly reproducible, as compared to traditionalindustrialize polymerizations. In some examples, the method can comprisereacting, via a second ring-opening polymerization within the flowreactor, an intermediate polymer with a second cyclic monomer in thepresence of a chemical compound to form a block copolymer. Theintermediate polymer can be formed from the polymerizing the cyclicmonomer. Also, the chemical compound can comprise a functional groupselected from a group consisting of a urea group and a thiourea group.An advantage of such a method can be that an active catalyst can beswitched during continuous processing of a copolymer to facilitatevarying chemical reaction rates.

According to an embodiment, a system is provided. The system cancomprise a flow reactor that can house a stream of chemical reactants tofacilitate a polymerization. The system can also comprise a memory thatstores computer executable components. Further, the system can comprisea processor, operably coupled to the memory, and that executes thecomputer executable components stored in the memory. The computerexecutable components can comprise an analysis component, operativelycoupled to the processor, that can control a parameter of the flowreactor based on a characteristic of a polymer produced by thepolymerization. An advantage of such a system can be that cognitivesoftware applications can facilitate discovery of novel chemicalcompounds and/or novel manufacturing techniques using continuousprocessing.

In some examples, the flow reactor can comprise a sensor that can detectthe characteristic. The parameter can affect a polymerization conditionof the polymerization. Also, the polymerization condition can beselected from a group consisting of a flow rate of the stream, aturbulence of the stream within the flow reactor, and an amount ofchemical reactants comprised within the stream. An advantage of such asystem can be optimization of one or more polymerization conditionswithin the flow reactor.

According to another embodiment, a method is provided. The method cancomprise forming a polyester by a ring-opening polymerization of acyclic monomer in the presence of an organocatylst comprising an anion.The ring-opening polymerization can be performed within a flow reactor.An advantage of such a method can be that one or more polyesters can beformed via continuous processing rather than traditional batchprocessing techniques. In some examples, the anion can be selected froma group consisting of a urea anion and a thiourea anion. An advantage ofsuch a method can be that the selected anion can facilitate polyesterreaction rates that can be substantially shorter than reaction ratesachieved via traditional polymerization conditions.

According to another embodiment, a method is provided. The method cancomprise forming a polycarbonate by a ring-opening polymerization of acyclic monomer in the presence of an organocatylst comprising an anion.The ring-opening polymerization can be performed within a flow reactor.An advantage of such a method can be that one or more polycarbonates canbe formed via continuous processing rather than traditional batchprocessing techniques. In some examples, the cyclic monomer can be acyclic carbonate monomer. Also, the anion can be selected from a groupconsisting of a urea anion and a thiourea anion. An advantage of such amethod can be that the selected anion can facilitate polycarbonatereaction rates that can be substantially shorter than reaction ratesachieved via traditional polymerization conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a diagram of example, non-limiting polymerizationschemes that can comprise one or more ring-opening polymerizationswithin one or more flow reactors in accordance with one or moreembodiments described herein.

FIG. 2A illustrates a diagram of example, non-limiting deprotonationschemes that can form one or more anionic catalysts, which canfacilitate one or more ring-opening polymerizations within one or moreflow reactors in accordance with one or more embodiments describedherein.

FIG. 2B illustrates a diagram of example, non-limiting functional groupsthat can be comprised within one or more anionic catalysts, which canfacilitate one or more ring-opening polymerizations within one or moreflow reactors in accordance with one or more embodiments describedherein.

FIG. 2C illustrates a diagram of example, non-limiting cyclic monomersthat can be polymerized with one or more urea anion catalysts and/or oneor more thiourea anion catalysts to facilitate one or more ring-openingpolymerizations within one or more flow reactors in accordance with oneor more embodiments described herein.

FIG. 3 illustrates a diagram of example, non-limiting deprotonationreactions that can form one or more urea anion catalysts, which canfacilitate one or more ring-opening polymerizations within one or moreflow reactors in accordance with one or more embodiments describedherein.

FIG. 4 illustrates a diagram of example, non-limiting deprotonationreactions that can form one or more thiourea anion catalysts, which canfacilitate one or more ring-opening polymerizations within one or moreflow reactors in accordance with one or more embodiments describedherein.

FIG. 5 illustrates a diagram of an example, non-limiting chart that candepict a relationship between acidity and catalytic activity regardingone or more anionic catalysts, which can facilitate one or morering-opening polymerizations within one or more flow reactors inaccordance with one or more embodiments described herein.

FIG. 6 illustrates a diagram of example, non-limiting polymerizationschemes that can facilitate forming one or more block copolymers via oneor more ring-opening polymerizations within one or more flow reactors inaccordance with one or more embodiments described herein.

FIG. 7A illustrates a diagram of an example, non-limiting polymerizationthat can facilitate forming one or more block copolymers via one or morering-opening polymerizations within one or more flow reactors inaccordance with one or more embodiments described herein.

FIG. 7B illustrates a diagram of an example, non-limiting protontransfer that can facilitate switching from one urea anion catalyst toanother urea anion catalyst to facilitate multiple ring-openingreactions within one or more flow reactors in accordance with one ormore embodiments described herein.

FIG. 8 illustrates a flow diagram of an example, non-limiting methodthat can facilitate forming a block copolymer via a plurality ofring-opening polymerization within one or more flow reactors, whereinthe plurality of ring-opening polymerizations can be facilitated by achanging an active catalyst from a first urea anion catalyst to a secondurea anion catalyst in accordance with one or more embodiments describedherein.

FIG. 9 illustrates a flow diagram of an example, non-limiting methodthat can facilitate forming a block copolymer via a plurality ofring-opening polymerization within one or more flow reactors, whereinthe plurality of ring-opening polymerizations can be facilitated by achanging an active catalyst from a first thiourea anion catalyst to asecond thiourea anion catalyst in accordance with one or moreembodiments described herein.

FIG. 10 illustrates a flow diagram of an example, non-limiting methodthat can facilitate forming one or more polyesters via a plurality ofring-opening polymerization within one or more flow reactors, whereinthe plurality of ring-opening polymerizations can be facilitated by anorganocatalyst in accordance with one or more embodiments describedherein.

FIG. 11 illustrates a flow diagram of an example, non-limiting methodthat can facilitate forming one or more polycarbonates via a pluralityof ring-opening polymerization within one or more flow reactors, whereinthe plurality of ring-opening polymerizations can be facilitated by anorganocatalyst in accordance with one or more embodiments describedherein

FIG. 12A illustrates a diagram of an example, non-limiting system thatcan facilitate autonomous control of one or more flow reactors tooptimize polymerization conditions in accordance with one or moreembodiments described herein.

FIG. 12B illustrates a diagram of an example, non-limiting system thatcan facilitate autonomous control of one or more flow reactors tooptimize polymerization conditions of one or more ring-openingpolymerizations within the one or more flow reactors in accordance withone or more embodiments described herein.

FIG. 13 depicts a cloud computing environment in accordance with one ormore embodiments described herein.

FIG. 14 depicts abstraction model layers in accordance with one or moreembodiments described herein.

FIG. 15 illustrates a block diagram of an example, non-limitingoperating environment in which one or more embodiments described hereincan be facilitated.

DETAILED DESCRIPTION

The following detailed description is merely illustrative and is notintended to limit embodiments and/or application or uses of embodiments.Furthermore, there is no intention to be bound by any expressed orimplied information presented in the preceding Background or Summarysections, or in the Detailed Description section.

One or more embodiments are now described with reference to thedrawings, wherein like referenced numerals are used to refer to likeelements throughout. In the following description, for purposes ofexplanation, numerous specific details are set forth in order to providea more thorough understanding of the one or more embodiments. It isevident, however, in various cases, that the one or more embodiments canbe practiced without these specific details.

Given the above problems with conventional techniques for polymerizingchemical compounds with batch processing; the present disclosure can beimplemented to produce a solution to one or more of these problems inthe form of a continuous production technique that can utilizeorganocatalysts within a flow reactor to produce one or more polymers(e.g., polyesters and/or polycarbonates). Continuous flow productiontechniques can take advantage of miniaturization, improved kineticcontrol, and/or expanded temperature ranges to circumvent many of thedisadvantages associated with batch processing (e.g., long productiontimes associated with heating and/or cooling batch reactors). Thus,continuous flow production designs can allow for: effective heattransfer, effective mixing, waste minimization, real time analysis,cleaner chemical products, novel chemical reactions, ease ofscalability, and/or short reaction times. Further, one or more systemsdescribed herein can advantageously control and/or manipulatepolymerization conditions of a flow reactor to: solve problems ofreproducibility traditionally exhibited by batch processing, optimizepolymerization conditions, and/or facilitate discovery of novel chemicalcompounds.

One or more embodiments described herein can regard forming homopolymersof polyesters and/or polycarbonates via one or more ring-openingpolymerizations (“ROP”) conducted within one or more flow reactors. Forexample, the one or more ROPs can comprise polymerizing one or morecyclic monomers (e.g., one or more lactone monomers and/or one or morecyclic carbonate monomers) in the presence of a urea anion catalyst(e.g., derived from a reaction with a chemical base). In anotherexample, the one or more ROPs can comprise polymerizing one or morecyclic monomers (e.g., one or more lactone monomers and/or one or morecyclic carbonate monomers) in the presence of a thiourea anion catalyst(e.g., derived from a reaction with a chemical base). Thus, one or moreembodiments can regard a continuous flow production of polyesters and/orpolycarbonates via one or more ROPs within one or more flow reactors;wherein, as compared to traditional batch production techniques, thecontinuous flow production can achieve faster reaction times, a narrowerdispersity of polymers, and/or tunable control over molecular weightdistributions.

Additionally, use of urea anion catalysts and/or thiourea anioncatalysts can provide a wide range of organocatalyst compounds, whichcan thereby provide a wide range of available catalytic activity. One ormore embodiments can regard utilizing the wide range of availablecatalytic activity to facilitate the formation of multiblock copolymersvia continuous flow productions, such as multiple ROPs within one ormore flow reactors. For example, a first block of a given blockcopolymer can be polymerized via ROP within a flow reactor, which can befacilitated by a first urea anion catalyst and/or thiourea anioncatalyst. A second block of the given block copolymer can be polymerizedvia another ROP within the flow reactor, which can be facilitated by asecond urea anion catalyst and/or thiourea anion catalyst. A switch ofthe active catalyst from the first urea anion catalyst and/or thioureaanion catalyst to the second urea anion catalyst and/or thiourea anioncatalyst can be performed via a proton transfer reaction conductedwithin the flow reactor. By switching the active catalyst, the catalyticactivity within the flow reactor can be adjusted based on the cyclicmonomer subject to ROP, wherein different cyclic monomers can be subjectto ROP at different stages of flow through the flow reactor. In otherwords, a stream of chemical reactants can flow through the flow reactorthereby undergoing one or more ROPs to form a multiblock copolymer,wherein one or more additional chemical reactants can be injected intothe flowing stream to facilitate formation of a block of the copolymerand/or a switch of the active catalyst.

Further, various embodiments of the present invention can be directed tocomputer processing systems, computer-implemented methods, apparatusand/or computer program products that facilitate the efficient,effective, and autonomous (e.g., without direct human guidance) controlof one or more flow reactors to optimize polymerization conditions thatcan facilitate one more ROPs within the one or more flow reactors. Theone or more ROPS within the one or more autonomously controlled flowreactors can facilitate the continuous production of, for example,polyesters and/or polycarbonates using anionic organocatalysts such asurea anion catalysts and/or thiourea anion catalysts. For example, oneor more embodiments can regard one or more systems that can comprise oneor more computer executable components that can facilitate autonomouscontrol of one or more flow reactors to optimize polymerizationconditions and/or discover various polymer compositions.

As used herein, the term “flow reactor” can refer to a device in whichone or more chemical reactions can take place within one or morechannels (e.g., microfluidic channels). For example, a flow reactor canfacilitate continuous flow production, as opposed to batch production.One or more streams of chemical reactants can flow (e.g., continuously)through the one or more channels of the flow reactor, wherein one ormore chemical reactions (e.g., polymerizations, protonations, and/ordeprotonations) involving the chemical reactants can occur within theone or more channels as the one or more streams flow.

As used herein, the term “urea anion catalyst” can refer to anorganocatalyst comprising one or more urea anions. For example, a ureaanion catalyst can comprise a molecular backbone having one or more ureaanions bonded (e.g., covalently) to one or more functional groups. Asused herein, the term “thiourea anion catalyst” can refer to anorganocatalyst comprising one or more thiourea anions. For example, athiourea anion catalyst can comprise a molecular backbone having one ormore thiourea anions bonded (e.g., covalently) to one or more functionalgroups.

FIG. 1 illustrates a diagram of example, non-limiting polymerizationschemes that can facilitate ROP of one or more cyclic monomers withinone or more flow reactors 100 in accordance with one or more embodimentsdescribed herein. For example, the plurality of polymerization schemesdepicted in FIG. 1 can comprise ROP of lactone monomers 102 and/orcyclic carbonate monomers 104 within one or more flow reactors 100(e.g., via a continuous flow production). Catalyst choice can directlyaffect the control over the one or more ROPs as well as the potentialfor deleterious transesterification reactions on the molecular backboneof produced polymers (e.g., homopolymers and/or copolymers), causing abroadening of the molecular weight distribution. Additionally, catalystchoice can determine the kinetics of polymerization and hence theresidence times in the one or more flow reactors, affecting overallreactor throughput.

The one or more ROPs depicted via the polymerization schemes of FIG. 1can comprise one or more urea anion catalysts 106 and/or the one or morethiourea anion catalysts 108. The one or more urea anion catalysts 106and/or the one or more thiourea anion catalysts 108 can afford highselectivity and/or control over the ROPs within the one or more flowreactors 100. Additionally, the one or more urea anion catalysts 106and/or the one or more thiourea anion catalysts 108 can exhibit veryfast kinetics of polymerization, thereby potentially allowing for veryshort reactor residence times. Moreover, the reactivity of one or morecyclic monomers (e.g., one or more lactone monomers 102 and/or one ormore cyclic carbonate monomers 104) can be matched with an appropriateurea anion catalyst 106 and/or thiourea anion catalyst 108 to facilitatecontrolled polymerization and minimization of molecular backbonetransesterification.

Additionally, the one or more ROPs depicted via the polymerizationschemes of FIG. 1 can be performed at room temperature. Further, the oneor more ROPs depicted via the polymerization schemes of FIG. 1 can becharacterized by residence times within the one or more flow reactors100 ranging from, for example, greater than or equal to 0.006 secondsand less than or equal to 3.5 seconds. Moreover, the one or more ROPsdepicted via the polymerization schemes of FIG. 1 can produce productscharacterized by narrow molecular weight distributions (Ð) ranging from,for example, greater than or equal to 1.07 and less than or equal to1.15.

A first polymerization scheme 109 can comprise ROP of one or morelactone monomers 102 in the presence of one or more urea anion catalysts106 (e.g., derived from and/or one or more chemical bases) to produceone or more polyesters 111. In one or more embodiments, the one or moreurea anion catalysts 106 can be derived from one or more chemical bases.However, one of ordinary skill in the art will recognize that the one ormore urea anion catalysts 106 can be derived through a variety ofmethodologies. As shown in the first polymerization scheme 109, the oneor more lactone monomers 102 can optionally comprise one or more firstfunctional groups (e.g., represented by “R¹”). Example first functionalgroups can include, but are not limited to: alkyl groups, aryl groups,substituted aryl groups, trifluoromethyl groups, phenyl groups, acombination thereof, and/or the like. Further, “n” can be an integer,for example, that is greater than or equal to zero (e.g., 1 or 2), so asto include five-member rings as well as macrocyclic lactones.Additionally, “m” can be an integer ranging, for example, from greaterthan or equal to 1 and less than or equal to 1000. Example lactonemonomers can include, but are not limited to: ε-caprolactone,δ-valerolactone, iPr-phosphonate, and/or lactide. One of ordinary skillin the art will recognize that the chemical structure for the one ormore lactone monomers 102 shown in FIG. 1 is exemplary and the one ormore lactone monomers 102 can be characterized by a wide variety ofchemical structures that comprise an ester group as part of a ringformation.

The one or more urea anion catalysts 106 can comprise a secondfunctional group (e.g., represented by “R²” in FIG. 1) and/or a thirdfunctional group (e.g., represented by “R³” in FIG. 1). Example secondand/or third functional groups can include, but are not limited to:alkyl groups, aryl groups, substituted aryl groups, trifluoromethylgroups, phenyl groups, a combination thereof, and/or the like. The oneor more urea anion catalysts 106 can be ionized in the presence of theone or more chemical bases. The one or more chemical bases can compriseorganic bases and/or strong metal containing bases. Example chemicalbases can include, but are not limited to:1,8-diazabicyclo[5.4.0]undec-7-ene (“DBU”),7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (“MTBD”), phosphazenebases, 1,3,2-diazaphosphorin-2-amin,2-[(1,1-dimethylethyl)imino]-N,N-diethyl-1,2,2,2,3,4,5,6-octahydro-1,3-dimethyl(“BEMP”), 1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene(“IMes”), potassium methoxide, potassium hydride, sodium methoxide,sodium hydride, a combination thereof, and/or the like.

The one or more flow reactors 100 can comprise, for example, one or moreinlets 112, one or more channels 114, one or more reactor loops 116,and/or one or more outlets 118. The one or more channels 114 can extendfrom the one or more inlets 112 to the one or more outlets 118. The oneor more channels 114 (e.g., microfluidic channels) can comprise, forexample: tubes (e.g., microfluidic tubes), pipes, joiners (e.g.,T-mixers), a combination thereof, and/or the like. Additionally, the oneor more channels 114 can be oriented into one or more reactor loops 116at one or more stages between the one or more inlets 112 and/or the oneor more outlets 118. The one or more reactor loops 116 can influence thelength of the one or more flow reactors 100 and thereby the residencetime of the one or more ROPs within the one or more flow reactors 100.One of ordinary skill in the art will recognize that the number of loopscomprising the reactor loops 116 and/or the dimensions of the loops canvary depending on a desired flow rate, residence time, and/orturbulence. Further, while the reactor loops 116 are depicted in FIG. 1as characterized by circular shaped structures, the architecture of thereactor loops 116 is not so limited. For example, the one or morereactor loops 116 can be characterized by elliptical and/or polygonalshaped structures.

The one or more ROPs depicted via the first polymerization scheme 109can produce one or more polyesters 111. The one or more polyesters 111can comprise a fourth functional group (e.g., represented by “R⁴” inFIG. 1) that can be derived from the one or more chemical bases. Examplefourth functional groups can include, but are not limited to: alkylgroups, aryl groups, methyl groups, a combination thereof, and/or thelike.

In the first polymerization scheme 109, the one or more lactone monomers102 can enter the flow reactor 100 via one or more first inlets 112,while the one or more urea anion catalysts 106 and/or the one or morechemical bases can enter the flow reactor via one or more second inlets112. The one or more lactone monomers 102 can meet and/or mix with theone or more urea anion catalysts 106 and/or the one or more chemicalbases within the one or more channels 114 of the flow reactor 100;thereby forming a stream of chemical reactants. As the stream flowsthrough the flow reactor, one or more ROPs can be facilitated by the oneor more urea anion catalysts 106, whereby the one or more lactonemonomers 102 can be polymerized to form one or more polyesters 111(e.g., a homopolymer solution of polyesters 111).

The second polymerization scheme 120 exemplifies that one or morethiourea anion catalysts 108 can also be utilized to polymerize the oneor more lactone monomers 102 and produce the one or more polyesters 111.Similar to the one or more urea anion catalysts 106, the one or morethiourea anion catalysts 108 can comprise the second functional group(e.g., represented by “R²” in FIG. 1) and/or the third functional group(e.g., represented by “R³” in FIG. 1). In one or more embodiments, theone or more urea anion catalysts 106 can be derived from one or morechemical bases. However, one of ordinary skill in the art will recognizethat the one or more urea anion catalysts 106 can be derived through avariety of methodologies. Further, the one or more thiourea anioncatalysts 108 can also be activated in the presence of the one or morechemical bases. As shown in the second polymerization scheme 120, theone or more thiourea anion catalysts 108 can facilitate one or more ROPsof the one or more lactone monomers 102 within one or more flow reactors100 to produce one or more polyesters 111 (e.g., a homopolymer solutionof polyesters 111). Also, as shown in the second polymerization scheme120, “n” can be an integer ranging, for example, that is greater than orequal to zero, so as to include five-member rings as well as macrocycliclactones. Additionally, “m” can be an integer ranging, for example, fromgreater than or equal to 1 and less than or equal to 1000.

Furthermore, as shown in the third polymerization scheme 122 the one ormore urea anion catalysts 106 can facilitate one or more ROPs of the oneor more cyclic carbonate monomers 104 within one or more flow reactors100 to produce one or more polycarbonates 124. The one or more cycliccarbonate monomers 104 can comprise a fifth functional group (e.g.,represented by “R⁵” in FIG. 1) and/or a sixth functional group (e.g.,represented by “R⁶” in FIG. 1). Example fifth and/or sixth functionalgroups can include, but are not limited to: alkyl groups, aryl groups,methyl groups, phenyl groups, amide groups, amine groups, ketone groups,ester groups, carboxyl groups, alcohol groups, alkane groups, alkenegroups, alkyne groups, aldehyde groups, imine groups, thiol groups,thioester groups, ether groups, a combination thereof, and/or the like.One of ordinary skill in the art will recognize that the chemicalstructure for the one or more cyclic carbonate monomers 104 shown inFIG. 1 is exemplary and the one or more cyclic carbonate monomers 104can be characterized by a wide variety of chemical structures thatcomprise a carbonate group in a ring formation. As shown in the thirdpolymerization scheme 122, “n” can be an integer ranging, for example,from greater than or equal to 1 and less than or equal to 1000. Further,the one or more polycarbonates 124 can also comprise the fourthfunctional group, which can be derived from the chemical base.

Moreover, the fourth polymerization scheme 126 can exemplify that one ormore thiourea anion catalysts 108 can also be utilized to polymerize theone or more cyclic carbonate monomers 104 and produce the one or morepolycarbonates 124. As shown in the fourth polymerization scheme 126,“n” can be an integer ranging, for example, from greater than or equalto 1 and less than or equal to 1000.

Further, while FIG. 1 depicts the use of lactone monomers 102 and/orcyclic carbonate monomers 104 in ROPs with one or more urea anioncatalysts 106 and/or one or more thiourea anion catalysts 108 in one ormore flow reactors 100 to produce one or more polyesters 111 and/orpolycarbonates 124, the architecture of the ROPs is not so limited. Forexample, the one or more urea anion catalysts 106, one or more thioureaanion catalysts 108, and/or one or more flow reactors 100 can beutilized with various other types of cyclic monomers to produce one ormore polyesters 111 and/or polycarbonates 124. Example cyclic monomersthat can be utilized to practice the one or more embodiments describedherein can include, but are not limited to: lactone monomers 102, cycliccarbonate monomers 104, substituted cyclic carbonates, cyclicphospholane monomers, morpholinone monomers,tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone,2-thiepanone, derivatives thereof, combinations thereof, and/or thelike.

In one or more embodiments, the polymerization schemes depicted in FIG.1 can be performed via a continuous flow of chemical reactants throughthe one or more flow reactors 100. Also, for each of the polymerizationschemes depicted in FIG. 1, polymerization conditions (e.g., residencetime within the flow reactor 100, molecular weight distribution of oneor more polyesters 111, transesterification of the one or morepolyesters' 111 molecular backbone, reaction rate of the one or moreROPs, a combination thereof, and/or like) can be dependent on one ormore parameters of the flow reactor 100. Example parameters that caninfluence polymerization conditions can include, but are not limited to:length of the one or more channels 114, number of reactor loops 116,dimensions of the reactor loops 116, flow rate of the stream of chemicalreactants, structure of a chemical mixer, a combination thereof, and/orlike. For instance, a degree of mixing between the chemical reactants inthe stream housed by the flow reactor 100 (e.g., via the one or morechannels 114) can directly influence the molecular weight distributionof the products (e.g., the one or more polyesters 111 and/or the one ormore polycarbonates 124). The degree of mixing can be function ofturbulence generated within the stream as it flows through the flowreactor 100 and can be influenced by parameters such as internalstructure of the one or more channels 114 and/or the flow rate of thestream.

FIG. 2A illustrates a diagram of example, non-limiting deprotonationschemes that can facilitate activation and/or formation of the one ormore urea anion catalysts 106 and/or the one or more thiourea anioncatalysts 108 in accordance with one or more embodiments describedherein. Repetitive description of like elements employed in otherembodiments described herein is omitted for sake of brevity. Thedeprotonations depicted via the deprotonation schemes of FIG. 2A can beperformed at room temperature. Further, the deprotonations depicted viathe deprotonation schemes of FIG. 2A can be performed inside and/oroutside the one or more channels 114 of the one or more flow reactors100.

As shown in FIG. 2A, the first deprotonation scheme 200 can facilitateactivation and/or formation of the one or more urea anion catalysts 106.In the first deprotonation scheme 200, one or more urea chemicalcompounds 202 can be subject to deprotonation to form the one or moreurea anion catalysts 106. The one or more urea chemical compounds 202can be electrically neural (e.g., non-ionic). Further, the one or moreurea chemical compounds 202 can comprise one or more urea groups bondedto the one or more second functional groups (e.g., represented by “R²)and/or the one or more third functional groups (e.g., represented by“R³” again). The deprotonation depicted in the first deprotonationscheme 200 can be a quantitative, relative to the chemical base,deprotonation by the chemical base (e.g., wherein the chemical base is astrong metal-containing base, such as potassium methoxide) or can be apartial deprotonation by the chemical base (e.g., wherein the chemicalbase is an organic base, such as DBU). Example urea chemical compounds202 from which the one or more urea anion catalysts 106 can be derived,in accordance with the first deprotonation scheme 200, can include, butare not limited to: 1,3-bis[3,5-bis(trifluoromethyl)phenyl]urea;1-[3,5-bis(trifluoromethyl)phenyl]-3-[2-(trifluoromethyl)phenyl]urea;1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylurea;1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylurea,1-phenyl-3-[3-(trifluoromethyl)phenyl]urea; 1,3-diphenylurea; and/or1-cyclohexyl-3-phenylurea.

As shown in FIG. 2A, the second deprotonation scheme 204 can facilitateactivation and/or formation of the one or more thiourea anion catalysts108. In the second deprotonation scheme 204, one or more thioureachemical compounds 206 can be subject to deprotonation to form the oneor more thiourea anion catalysts 108. The one or more thiourea chemicalcompounds 206 can be electrically neural (e.g., non-ionic). Further, theone or more thiourea chemical compounds 206 can comprise one or morethiourea groups bonded to the one or more second functional groups(e.g., represented by “R²” again) and/or the one or more thirdfunctional groups (e.g., represented by “R³” again). The deprotonationdepicted in the second deprotonation scheme 204 can be a quantitative,relative to the chemical base, deprotonation by the chemical base (e.g.,wherein the chemical base is a strong metal-containing base, such aspotassium methoxide) or can be a partial deprotonation by the chemicalbase (e.g., wherein the chemical base is an organic base, such as DBU).Example thiourea chemical compounds 206 from which the one or morethiourea anion catalysts 108 can be derived, in accordance with thesecond deprotonation scheme 204, can include, but are not limited to:N,N′-di[3,5-di(trifluoromethyl)phenyl]thiourea;1-[3,5-bis(trifluoromethyl)phenyl]-3-[3-(trifluoromethyl)phenyl]thiourea;1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylthiourea;1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea;1-phenyl-3-[3-(trifluoromethyl)phenyl]thiourea; N,N′-diphenylthiourea;and/or 1-cyclohexyl-3-phenylthiourea

FIG. 2B illustrates a diagram of example, non-limiting functional groupsthat can characterize the structure of the one or more second functionalgroups (e.g., represented by “R²”) and/or the one or more thirdfunctional groups (e.g., represented by “R³”) in accordance with one ormore embodiments described herein. Repetitive description of likeelements employed in other embodiments described herein is omitted forsake of brevity. As shown in FIG. 2B, “X” can represent a urea groupand/or a thiourea group comprised within the one or more urea chemicalcompounds 202, the one or more urea anion catalysts 106, the one or morethiourea chemical compounds 206, and/or the one or more thiourea anioncatalysts 108. The chemical structures depicted in FIG. 2B cancharacterize the one or more first functional groups (e.g., representedby “R¹”), second functional groups (e.g., represented by “R²”), and/orthe one or more third functional groups (e.g., represented by “R³”).

FIG. 2C illustrates a diagram of example, non-limiting cyclic monomersthat can be polymerized with one or more urea anion catalysts 106 and/orone or more thiourea anion catalysts 108 to facilitate one or more ROPswithin one or more flow reactors in accordance with one or moreembodiments described herein. Repetitive description of like elementsemployed in other embodiments described herein is omitted for sake ofbrevity. FIG. 2C depicts exemplary cyclic monomers, in addition to theone or more lactone monomers 102 and/or cyclic carbonate monomers 104,that can undergo ROPs within one or more flow reactors 100 to synthesizeone or more polymers through the use of the one or more urea anioncatalysts 106 and/or thiourea anion catalysts 108 in accordance with thevarious embodiments described herein.

As shown in FIG. 2C, “n” can be an integer that is greater than or equalto one (e.g., 1 or 2). Moreover, “A” can represent a carbon bonded tothe second functional group (e.g., CR²), an oxygen, and/or a nitrogenbonded to the second functional group (e.g., NR²). In one or moreembodiments, the cyclic monomers can have five-member rings.

For instance, the one or more cyclic monomers can include, but are notlimited to: lactone monomers 102, cyclic carbonate monomers 104,substituted cyclic carbonates, cyclic phospholane monomers, morpholinonemonomers, tetrahydro-2H-pyran-2-thione, oxepane-2-thione,tetrahydrothiopyranone, 2-thiepanone, derivatives thereof, combinationsthereof, and/or the like. One of ordinary skill in the art willrecognize that the chemical structure for the one or more cyclicmonomers shown in FIG. 2C is exemplary and the one or more cyclicmonomers can be characterized by a wide variety of chemical structures.

In one or more embodiments, the one or more features of the ROPsdepicted in FIGS. 1, 2A, and/or 2B (e.g., ROP comprising urea anioncatalysts 106 and/or thiourea anion catalysts 108 within one or moreflow reactors 100) can be utilized with the various cyclic monomersdepicted in FIG. 2C to produce a variety of polymers (e.g., homopolymersand/or copolymers). For example, the ROPs described in the variousembodiments herein can produce polythioesters, polyamides, and/orpolyphosphoesters in addition to the polyesters 111 and/orpolycarbonates 124. Additionally, these polythioesters, polyamides,and/or polyphosphoesters chemical products can comprise the fourthfunctional group (e.g., “R⁴”) described herein. For instance, one ofordinary skill in the art will recognize that the various cyclicmonomers described herein (e.g., depicted in FIG. 2C) can polymerize(e.g., in the presence of a urea anion catalyst 106 and/or a thioureaanion catalyst 108), within the one or more flow reactors 100, along acarbonyl oxygen and/or carbonyl-thiol bond that breaks during the ROP,thereby producing a growing oxygen-hydrogen (“OH”) or sulfur-hydrogen(“SH”) structure.

FIG. 3 illustrates a diagram of example, non-limiting deprotonationreactions that can facilitate activation and/or formation of the one ormore urea anion catalysts 106 in accordance with one or more embodimentsdescribed herein. Repetitive description of like elements employed inother embodiments described herein is omitted for sake of brevity. Forexample, the deprotonations depicted in FIG. 3 can exemplify thefeatures depicted and/or described with regards to FIGS. 2A, 2B, and/or2C.

As indicated by an arrow flanking the left side of FIG. 3, the exampleurea chemical compounds 202 are presented in order by decreasing acidityfrom the top of FIG. 3 to the bottom of FIG. 3. For example,1,3-bis[3,5-bis(trifluoromethyl)phenyl]urea is the most acidic ureachemical compound 202 presented in FIG. 3 and is thereby located at thetop of FIG. 3; whereas 1-cyclohexyl-3-phenylurea is the least acidicurea chemical compound 202 presented in FIG. 3 and is thereby presentedat the bottom of FIG. 3. As indicated by an arrow flanking the rightside of FIG. 3, the exemplary urea anion catalysts 106 are presented inorder by increasing catalytic activity (e.g., with regards to at leastthe ROPs characterized by the first polymerization scheme 109 and thethird polymerization scheme 122) from the top of FIG. 3 to the bottom ofFIG. 3. For example, the urea anion catalyst 106 derived from1,3-bis[3,5-bis(trifluoromethyl)phenyl] urea exhibits the leastcatalytic activity of the urea anion catalysts 106 presented in FIG. 3and is thereby located at the top of FIG. 3; whereas the thiourea anioncatalyst 108 derived from 1-cyclohexyl-3-phenylurea exhibits the mostcatalytic activity of the urea anion catalysts 106 presented in FIG. 3and is thereby presented at the bottom of FIG. 3. Thus, as illustratedin FIG. 3, as acidity of the one or more urea chemical compounds 202decreases, the catalytic activity of the corresponding urea anioncatalysts 106 increases.

Amongst the plurality of urea anion catalysts 106 presented in FIG. 3, adifference between the catalytic activity of the most reactive ureaanion catalyst 106 and the least reactive urea anion catalyst 106 canreach up to ten orders of magnitude. Thus, the one or morepolymerization schemes described herein (e.g., first polymerizationscheme 109 and/or third polymerization scheme 122) can use one or moreurea anion catalysts 106 based on the cyclic monomer being polymerized.For example, the selection of a urea anion catalyst 106 to be utilizedin a subject ROP can be catered to cyclic monomers of differentreactivity and/or stability. Therefore, one or more polymerizationconditions (e.g., conversion rate and/or molecular weight dispersity)can be adjusted by varying the urea anion catalyst 106 identity and/orconcentration without changing one or more parameters of the flowreactor 100.

FIG. 4 illustrates a diagram of example, non-limiting deprotonationreactions that can facilitate activation and/or formation of the one ormore thiourea anion catalysts 108 in accordance with one or moreembodiments described herein. Repetitive description of like elementsemployed in other embodiments described herein is omitted for sake ofbrevity. For example, the deprotonations depicted in FIG. 4 canexemplify the features depicted and/or described with regards to FIGS.2A, 2B, and/or 2C.

As indicated by an arrow flanking the left side of FIG. 4, the examplethiourea chemical compounds 206 are presented in order by decreasingacidity from the top of FIG. 4 to the bottom of FIG. 4. For example,N,N′-di[3,5-di(trifluoromethyl)phenyl]thiourea is the most acidicthiourea chemical compound 206 presented in FIG. 4 and is therebylocated at the top of FIG. 4; whereas 1-cyclohexyl-3-phenylthiourea isthe least acidic thiourea chemical compound 206 presented in FIG. 4 andis thereby presented at the bottom of FIG. 4. As indicated by an arrowflanking the right side of FIG. 4, the exemplary thiourea anioncatalysts 108 are presented in order by increasing catalytic activity(e.g., with regards to at least the ROPs characterized by the secondpolymerization scheme 120 and the fourth polymerization scheme 126) fromthe top of FIG. 4 to the bottom of FIG. 4. For example, the thioureaanion catalyst 108 derived fromN,N′-di[3,5-di(trifluoromethyl)phenyl]thiourea exhibits the leastcatalytic activity of the thiourea anion catalysts 108 presented in FIG.4 and is thereby located at the top of FIG. 4; whereas the thioureaanion catalyst 108 derived from 1-cyclohexyl-3-phenylthiourea exhibitsthe most catalytic activity of the thiourea anion catalysts 108presented in FIG. 4 and is thereby presented at the bottom of FIG. 4.Thus, as illustrated in FIG. 4, as acidity of the one or more thioureachemical compounds 206 decreases, the catalytic activity of thecorresponding thiourea anion catalysts 108 increases.

Amongst the plurality of thiourea anion catalysts 108 presented in FIG.4, a difference between the catalytic activity of the most reactivethiourea anion catalyst 108 and the least reactive thiourea anioncatalyst 108 can reach up to ten orders of magnitude. Thus, the one ormore polymerization schemes described herein (e.g., secondpolymerization scheme 120 and/or fourth polymerization scheme 126) canuse one or more thiourea anion catalysts 108 based on the cyclic monomerbeing polymerized. For example, the selection of a thiourea anioncatalyst 108 to be utilized in a subject ROP can be catered to cyclicmonomers of different reactivity and/or stability. Therefore, one ormore polymerization conditions (e.g., conversion rate and/or molecularweight dispersity) can be adjusted by varying the thiourea anioncatalyst 108 identity and/or concentration without changing one or moreparameters of the flow reactor 100.

FIG. 5 illustrates a diagram of an example, non-limiting graph 500 thatcan depict a relationship between the acidity of urea anion catalysts106 and the catalytic activity of the urea anion catalysts 106 inaccordance with one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity. Acidity of the urea anioncatalysts 106 (e.g., and/or the thiourea anion catalysts 108) can be afunction of the number of trifluoromethyl groups comprised within theurea anion catalyst 106; wherein the higher the number oftrifluoromethyl groups present, the higher the acidity of the urea anioncatalyst 106 (e.g., and/or the thiourea anion catalyst 108). As shown ingraph 500, the first line 502 can represent the ROP of ε-caprolactone asthe lactone monomer 102 with the various exemplar urea anion catalysts106 presented in FIG. 3 in accordance with the first polymerizationscheme 109. The second line 504 can represent the ROP of δ-valerolactoneas the lactone monomer 102 with the various exemplar urea anioncatalysts 106 presented in FIG. 3 in accordance with the firstpolymerization scheme 109. The third line 506 can represent the ROP ofiPr-phosphonate as the lactone monomer 102 with the various exemplarurea anion catalysts 106 presented in FIG. 3 in accordance with thefirst polymerization scheme 109. The fourth line 508 can represent theROP of benzyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate as the cycliccarbonate monomer 104 with the various exemplar urea anion catalysts 106presented in FIG. 3 in accordance with the third polymerization scheme122. The fifth line 510 can represent the ROP of lactide as the lactonemonomer 102 with the various exemplar urea anion catalysts 106 presentedin FIG. 3 in accordance with the first polymerization scheme 109.

Table 1, presented below, comprises data regarding one or morepolymerization conditions for a ROP performed in accordance with the oneor more embodiments described herein (e.g., in accordance with thevarious features and/or descriptions associated with FIGS. 1-3 and 6).For example, Table 1 regards a polymerization performed in accordancewith the first polymerization scheme 109, wherein the one or morelactone monomers 102 were δ-valerolactone monomers, the one or more ureaanion catalysts 106 were derived from 1-cyclohexyl-3-phenylurea (e.g.,as depicted in FIG. 3), and the one or more chemical bases werepotassium methoxide.

In particular, a catalytic solution comprising 14 milligrams (mg) ofpotassium methoxide, 131 mg of the urea anion catalyst 106, and 4.9milliliters (mL) of tetrahydrofuran (“THF”), was added to a subject flowreactor 100 (e.g., via a first inlet 112). Additionally, a cyclicmonomer solution comprising 800 mg of δ-valerolactone and 4 mL of THFwas added to the subject flow reactor 100 (e.g., via a second inlet112). The two solutions were infused into the flow reactor 100 atvarious flow rates, as indicated in Table 1. The flow reactor 100 outputwas quenched directly with excess benzoic acid THF. Conversion wasmeasured by proton nuclear magnetic resonance (“¹H NMR) of quenchedpolymer samples. Molecular weight (“M_(n)”) was measured in kilodaltons(kDa) by gel permeation chromatography (“GPC”) using THF as the eluentand calibrated with polystyrene standards. The ROPs depicted by Table 1were performed at room temperature. The total flow rate of the stream ofchemical reactants (e.g., comprised within both solutions) was measuredin milliliters per minute (mL/min). The residence time of the stream ofchemical reactants within the flow reactor 100 was measured in seconds(s).

TABLE 1 Total Residence Flow Rate Time Entry (mL/min) (s) ConversionM_(n)(kDa) Ð 1 0.5 10 45% 19 1.58 2 1 10 71% 17 1.60 3 2 10 90% 16 1.814 2 5 74% 8.9 1.71 5 8 5 90% 9.8 1.63 6 8 0.6 79% 7.3 1.58 7 16 0.3 85%7.4 1.22 8 30 0.15 49% 4.9 1.13 9 30 0.8 86% 7.8 1.11

As shown in Table 1, lower flow rates led to substantial reductions inreaction rate compared to polymerization in batch, and broad molecularweight distributions of the obtained polymers. Increasing the flow rateled to substantially improved polymerization kinetics and control,thereby matching in-batch counterparts. As such subsequentpolymerizations were carried out at flow rates of 15 mL/min per inlet112.

For example, Table 2, presented below, comprises data regarding one ormore polymerization conditions for a ROP performed in accordance withthe one or more embodiments described herein (e.g., in accordance withthe various features and/or descriptions associated with FIGS. 1-3 and6). For example, Table 2 regards a polymerization performed inaccordance with the first polymerization scheme 109, with a variety oflactone monomers 102, a variety of urea anion catalysts 106, andpotassium methoxide used as the chemical base. The cyclic monomers arepresented with their molar concentration (M), wherein “LA” representslactide, “VL” represents δ-valerolactone, “CL” representsε-Caprolactone, and “TMC-Bn” represents benzyl5-methyl-2-oxo-1,3-dioxane-5-carboxylate. As shown in Table 2, “[M]/[I]”can represent a ratio of monomer to initiator (e.g., urea anion catalyst106). Additionally, the polymerizations performed with flow rates of 15mL/min per inlet 112 at room temperature. Moreover, urea “#3” canrepresent the urea anion catalyst 106 derived from1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylurea as shown in FIG. 3, urea“#5” can represent the urea anion catalyst 106 derived from1-phenyl-3-[3(trifluoromethyl)phenyl]urea as shown in FIG. 3, and urea“#7” can represent the urea anion catalyst 106 derived from1-cyclohexyl-3-phenylurea as shown in FIG. 3. Further, the initiatorsolution used in the polymerizations depicted by Table 2 can comprise achemical base to urea anion catalyst 106 ratio of 1:3; except for entry3, which had a chemical base to urea anion catalyst 106 ratio of 1:1.5.Moreover, the polymerization of entry 6 utilized a flow rate of 24mL/min per inlet 112.

TABLE 2 Residence Conver- M_(n) Entry Monomer [M]/[I] Urea Time (s) sion(kDa) Ð 1 LA (0.5M) 25 3 0.32 96% 5.4 1.13 2 LA (1M) 50 3 0.32 98% 131.09 3 LA (1M) 50 5 0.03 92% 14 1.09 4 LA (1M) 100 3 1.3 98% 25 1.11 5VL (1M) 50 7 0.81 86% 7.8 1.11 6 CL (1M) 50 7 2.3 91% 9.1 1.14 7 TMC-Bn50 5 0.04 89% 11 1.15

While batch polymerizations of LA were traditionally performed with theless active urea catalysts, more active urea anion catalysts 106 (e.g.,urea #3 and/or #5) can be used in the flow reactor 100 presumably due tomore efficient mixing and quenching. In entry 2, the polymerization ofLA reached 98% conversion in just 0.32 s to yield poly(LA) with a narrowmolecular weight distribution (e.g., Ð=1.09). More extraordinarily, inentry 3 and a reactor length of 3 centimeters (cm) (e.g., 3 cm of theone or more channels 114 extending from the one or more inlets 112 tothe one or more outlets 118), the polymerization of LA reached 92%conversion in just 30 milliseconds (ms) with the same degree of control(e.g., Ð=1.09). Such short reaction times together with the high degreeof control is not feasible in traditional batch production. Forinstance, tor VL, a monomer over 250 times less reactive than LA towardsROP, the most catalytically active urea anion catalyst 106 (e.g., urea#7) catalyzed its polymerization to 86% conversion in 0.8 s to generatea well-defined poly(VL) (e.g., Ð=1.11). Using the same catalyst system,the ROP of CL (6200 times less reactive than LA) reached 91% conversion,with control similar to its batch counterpart (e.g., Ð=1.14). With atotal flow rates of 30 mL/min or 48 mL/min, each of these reactor setupsgenerates polymers at the rate of multiple grams per minute.

To exemplify one or more features of the polymerizations depicted inFIG. 1, entry 4 of Table 2 was synthesized in accordance with the firstpolymerization scheme 109 under the following exemplary conditions. Inan N₂-filled glovebox, a solution of L-LA having a molar concentrationof 2 mol/L (M) was prepared by dissolving 1440 mg L-LA in 3.6 mL of THF.A catalyst and initiator solution was prepared by dissolving 7 mg KOMeand 104 mg urea #3 in 4.9 mL THF and then filtered through a syringefilter. Both solutions were transferred to 5-mL syringes respectively.Outside of the glovebox, after dry THF was flowed through the reactorvia syringes, the syringes containing the monomer solution andcatalyst/initiator solution were connected to the flow reactor 100. Thesyringe pump was set to a flow rate of 15 mL/min for each inlet 112, andthe solutions were combined via a generic 0.0157 cm diameter T-mixer,with a total flow rate of 30 mL/min. The one or more channels 114 (e.g.,tubing) to facilitate the polymerization was 60 cm long with a 0.0157 cmdiameter, corresponding to a residence time of 1.3 seconds. Thepolymerization was quenched by directing the reaction mixture into abath of benzoic acid in THF.

FIG. 6 illustrates a diagram of example, non-limiting polymerizationschemes that can facilitate synthesis of one or more copolymers (e.g.,block copolymers) via one or more ROP conducted within one or more flowreactors 100 in accordance with one or more embodiments describedherein. Repetitive description of like elements employed in otherembodiments described herein is omitted for sake of brevity. Thepolymerizations depicted in FIG. 6 comprise many of the same featuresdescribed with regards to FIG. 1, but with an additional step tofacilitate the synthesis of block copolymers. The matching of cyclicmonomer and catalyst reactivity enables a catalyst switch approach forblock copolymer synthesis using cyclic monomers with disparatereactivity profiles. For example, an active urea anion catalyst 106 forpolymerization of the first block is quenched by the addition of aneutral urea chemical compound 202 via a proton transfer to generate anew urea anion catalyst 106 with a different catalytic activity for thepolymerization of the second block. In another example, an activethiourea anion catalyst 108 for polymerization of the first block isquenched by the addition of a neutral thiourea chemical compound 206 viaa proton transfer to generate a new thiourea anion catalyst 108 with adifferent catalytic activity for the polymerization of the second block.

The syntheses of well-defined block copolymers can be important for manymaterial applications, including the generation of nanoparticles andfunctional bioactive polymers. Under traditional batch polymerizationconditions, the synthesis of block copolymers with narrow molecularweight distributions can be challenging. The polymerization, isolation,and purification of the block copolymer intermediates can be tedious andtime consuming for multi-step synthetic processes. Whereas synthesizingblock copolymers in one container relies on the efficient addition andmixing of monomers for each sequential block. The utilization of flowreactors 100 (e.g., via continuous flow polymerization) offers anexcellent alternative to traditional batch procedures for thepreparation multi-block polymers as the monomers for each block can beseamlessly introduced in sequential stages of one or more flow reactors100 with highly efficient mixing.

For example, with regards to the fifth polymerization scheme 602, ROP ofthe one or more lactone monomers 102 and the one or more urea anioncatalysts 106 can produce an intermediate polymer that can serve as thefirst block of a multiblock copolymer. The intermediate polymer can befurther polymerized by the introduction of an additional lactone monomer102. For example, the additional lactone monomer 102 can enter the flowreactor 100 via a third inlet 112 and can mix with a stream of theintermediate polymer in the one or more channels 114 of the flow reactor100.

Additionally, in one or more embodiments, one or more urea chemicalcompounds 202 can enter the flow reactor 100 (e.g., via the third inlet112) to facilitate a switch of the active urea anion catalyst 106. Forexample, the urea chemical compound 202 can mix in the one or morechannels 114 with the urea anion catalyst 106 used to synthesize theintermediate polymer; thereby initiating a proton transfer that canneutralize the urea anion catalyst 106 and ionize the urea chemicalcompound 202. In effect, introducing the additional urea chemicalcompound 202 to the stream comprising the intermediate polymer cantransform the urea anion catalyst 106 to a urea chemical compound 202and the additional urea chemical compound 202 to a urea anion catalyst106; thereby switching the active catalyst from one exemplary urea anioncatalyst to another.

The sixth polymerization scheme 604, which can be a modification to thesecond polymerization scheme 120, can exemplify the catalyst switchusing thiourea anion catalysts 108. For example, a first thiourea anioncatalyst 108 can facilitate a first ROP of a first lactone monomer 102,which can serve as a first block of a copolymer, and then can beprotonated by a thiourea chemical compound 206 in another stage of theflow reactor 100. The protonation can quench the first thiourea anioncatalyst 108 and simultaneously form a second thiourea anion catalyst108 from the thiourea chemical 206, wherein the second thiourea anioncatalyst 108 can facilitate a second ROP of a second lactone monomer 102that can serve as a second block of the copolymer.

Similarly, the seventh polymerization scheme 606 and/or the eighthpolymerization scheme 608 can exemplify the catalyst switch techniqueswith regards to cyclic carbonate monomers 104. One of ordinary skill inthe art will recognize that the chemical structure for the one or morelactone monomers 102 shown in FIG. 6 is exemplary and the one or morelactone monomers 102 can be characterized by a wide variety of chemicalstructures that comprise an ester group as part of a ring formation.Additionally, one of ordinary skill in the art will recognize that thechemical structure for the one or more cyclic carbonate monomers 104shown in FIG. 6 is exemplary and the one or more cyclic carbonatemonomers 104 can be characterized by a wide variety of chemicalstructures that comprise a carbonate group in a ring formation. In eachof the polymerization schemes shown in FIG. 6, “n” can respectively bean integer ranging, for example, that is greater than or equal to zero(e.g., 1 or 2), so as to include five-member rings as well asmacrocyclic lactones.

Each of the exemplary polymerization schemes shown in FIG. 6 compriseROP of respective cyclic monomers (e.g., a first lactone monomer 102 andsecond lactone monomer 102 in the fifth polymerization scheme 602 and/orthe sixth polymerization scheme 604, and/or a first cyclic carbonatemonomer 104 and a second cyclic carbonate monomer 104 in the seventhpolymerization scheme 606 and/or the eighth polymerization scheme 608),which each respective cyclic monomer in a given polymerization schemecan be characterized by a different chemical structure. Additionally,wherein a polymerization scheme can include a catalyst switch (e.g., asdepicted in the polymerization schemes of FIG. 6), the initial anionicorganocatalyst (e.g., a urea anion catalyst 106 and/or a thiourea anioncatalyst 108) can be derived from a chemical compound (e.g., a ureachemical compound 202 and/or a thiourea chemical compound 206) that isdifferent that the chemical compound (e.g., a urea chemical compound 202and/or a thiourea chemical compound 206) introduced into the flowreactor 100 to facilitate the catalyst switch. In one or moreembodiments, the polymerization schemes depicted in FIG. 6 can beperformed via a continuous flow of chemical reactants through the one ormore flow reactors 100.

In one or more embodiments, the one or more of the polymerizationschemes depicted in FIG. 6 can include a ROP of a lactone monomer 102 toform one block of a copolymer and/or another ROP of a cyclic carbonatemonomer 104 to form another block of the copolymer. Also, in one or moreembodiments, an initial urea anion catalyst 106 can be protonated by athiourea chemical compound 206; thereby facilitating a catalyst switchfrom a urea anion catalyst 106 to a thiourea anion catalyst 108.Further, in one or more embodiments an initial thiourea anion catalyst108 can be protonated by a urea chemical compound 202; therebyfacilitating a catalyst switch from a thiourea anion catalyst 108 to aurea anion catalyst 106.

FIG. 7A illustrates a diagram of an example, non-limiting polymerizationthat can be performed in accordance with the fifth polymerization scheme602 and/or in accordance with one or more embodiments described herein.Repetitive description of like elements employed in other embodimentsdescribed herein is omitted for sake of brevity. In one or moreembodiments, the polymerization of FIG. 7A can be performed at roomtemperature and/or in a continuous flow of the chemical reactants in astream through the one or more flow reactors 100.

FIG. 7B illustrates a diagram of an example, non-limiting protonation tthat can occur in the polymerization depicted in FIG. 7A in accordancewith one or more embodiments described herein. Repetitive description oflike elements employed in other embodiments described herein is omittedfor sake of brevity. FIG. 7B can depict an exemplary catalyst switchthat can facilitate the polymerization depicted in FIG. 7A. Because theactive catalysts are anions, they can be protonated by neutral ureachemical compounds 202 and/or neutral thiourea chemical compounds 206,the equilibrium of which can be dictated by their relative acidities.Therefore, adding a more acidic urea chemical compound 202 and/orthiourea chemical compound 206 (e.g.,1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylurea) to the anion of a morebasic urea anion catalyst 106 and/or thiourea anion catalyst 108 willprotonate the more basic anion, and simultaneously generate a lessactive urea anion catalyst 106 and/or thiourea anion catalyst 108 (e.g.,as shown in FIG. 7B), allowing for matching of the catalyst and monomerreactivity.

In traditional ROPs, a main challenge can exist when the blocks are madefrom monomers with very different reactivity. For example, the rate ofLA polymerization has been observed to be ˜250 times faster than VL. Forinstance, the use of a single urea anion catalyst 106 in flow for thesynthesis of a VL₅₀-LA₅₀ block copolymer, would result in the residencetime for the VL block being over 2 orders of magnitude longer than theLA block. This would potentially allow for transesterification of thepolymer backbone as a result of using increased residence times and amore active urea anion catalyst 106. However, the acidity-basedreactivity of the urea anion catalysts 106 and/or the thiourea anioncatalysts 108 can overcome these challenges. More acidic urea anionslead to slower reactions, which was proposed to be due to the weakernucleophilic activation of the initiator or propagating chain end. Byselecting the appropriate catalysts for each cyclic monomer, comparableretention time of the blocks can be achieved and transesterification canbe minimized. Since proton exchange should be much faster compared tothe ring-opening of monomers, the urea chemical compound 202 and/or thethiourea chemical compound 206 for the subsequent block can be injectedinto the reactor with the cyclic monomer, instead of through anadditional dedicated inlet 112.

Table 3 presents data regarding the polymerization ofpoly(VL₅₀)-b-(LA₅₀) depicted in FIG. 7A as compared to polymerization ofthe block copolymer under alternative polymerization conditions. Theflow rate for the polymerization was 15 mL/min per inlet 112. Thediameter of the one or more channels 114 of the one or more flowreactors 100 were 1 millimeter (mm). The conversion depicted in Table 3was measured by ¹H NMR. Further, the first block was prepared using aratio of potassium methoxide:urea #7:VL equal to 1:3:50. The reactiontime for the VL block was 0.81 s and the reaction time for the LA blockwas 0.43 s for a total of 1.24 s. Also, the molarity of VL for the firstblock was 1 M, and the molarity of LA for the second block was 2 M.

TABLE 3 Conversion Conversion Entry Conditions (VL) (LA) M_(n) (kDa) Ð 1In flow; 88% 93% 23 1.11 catalyst switch 2 In flow; 88% 97% 15 1.36 nocatalyst switch 3 In batch; 87% 96% 22 1.21 catalyst switch

As shown in Table 3, the synthesis of a poly(VL₅₀)-b-poly-(LA₅₀)copolymer using the catalyst switch strategy generated (e.g., asdepicted in FIG. 7A) a well-defined copolymer with a narrow molecularweight distribution (e.g. Ð=1.11). In contrast, when no catalyst switchwas employed, a much broader molecular weight distribution was obtained(e.g. Ð=1.36). The catalyst switch mechanism was also attempted in batchusing conditions similar to those in entry 1. However, a broadermolecular weight distribution was obtained due to the very shortreaction time (e.g., less than 1.5 s), where the manual addition of thesolutions and mixing can be problematic (e.g. Ð=1.21). Scaling up inbatch production under these conditions would not be ideal (e.g., due topoorer mixing in larger scale reactors).

To exemplify one or more features of the polymerizations depicted inFIG. 6, entry 1 of Table 3 was synthesized in accordance with the fifthpolymerization scheme 602 under the following exemplary conditions. Inan N₂-filled glovebox, a 2 M solution of VL was prepared by dissolving1000 mg of VL in 4 mL THF. A catalyst and initiator solution wasprepared by dissolving 7 mg of KOMe and 131 mg of urea #7 in 4.9 mL THFand then filtered through a syringe filter. A solution of L-LA and urea#3 was prepared by dissolving 1440 mg of L-LA and 208 mg of urea #3 in3.4 mL of THF. All the solutions were transferred to 5-mL syringesrespectively. Outside of the glovebox, after dry THF were flowed throughthe flow reactor via syringe injections, the syringes containing the VLsolution, the catalyst/initiator solution and the LA/urea #3 solutionswere connected to the flow reactor 100. The syringe pump was set to aflow rate of 15 mL/min for each inlet, and the solutions were combinedvia two generic 0.0157 cm diameter T-mixers, with a final total flowrate of 45 mL/min. The one or more channels 114 for VL polymerization is50 cm long with a 0.81 s residence time, and the one or more channels114 for LA polymerization is 70 cm long with a 0.0157 cm diameter,corresponding a residence time of 0.76 second. The polymerization wasquenched by directing the reaction mixture into a bath of benzoic acidin THF (equipped with a stir bar).

FIG. 8 illustrates a flow diagram of an example, non-limiting method 800that can facilitate the polymerization of polymers (e.g., homopolymersand/or block copolymers) via one or more ROP in one or more flowreactors 100 in accordance with one or more embodiments describedherein. Repetitive description of like elements employed in otherembodiments described herein is omitted for sake of brevity.

At 802 the method 800 can comprise selecting one or more organocatalystsfrom a plurality of organocatalysts comprising a urea anion based on areactivity rate of one or more cyclic monomers. For example, the one ormore selected organocatalyst can be urea anion catalysts 106. Further,the one or more cyclic monomers can be lactone monomers 102, cycliccarbonate monomers 104, and/or the cyclic monomers depicted in FIG. 2C.For instance, the plurality of organocatalysts (e.g., plurality of ureaanion catalysts 106) can be characterized be differing respectivecatalytic activities. In other words, a first organocatalyst (e.g., afirst urea anion catalyst 106) from the plurality of organocatalysts(e.g., from the plurality of urea anion catalysts 106) can be morereactive than a second organocatalyst (e.g., a second urea anioncatalyst 106) from the plurality of organocatalysts (e.g., from theplurality of urea anion catalysts 106). Thus, the selecting at 802 cancomprise selecting an organocatalyst (e.g., a urea anion catalyst 106)with similar reactivity as the subject one or more cyclic monomers.

At 804, the method 800 can comprise polymerizing, via a ROP within oneor more flow reactors 100, the one or more cyclic monomers in thepresence of the selected one or more organocatalysts comprising the ureaanion (e.g., the one or more selected urea anion catalysts 106). Forexample, the one or more selected organocatalysts can be one or more ofthe exemplary urea anion catalysts 106 presented in FIG. 3.

In one or more embodiments (e.g., regarding the polymerization of one ormore block copolymers), the method 800 can further comprise, at 806,reacting, via a second ROP within the flow reactor 100, an intermediatepolymer with a second cyclic monomer (e.g., a lactone monomer 102 and/ora cyclic carbonate monomer 104) in the presence of a chemical compound(e.g., a urea chemical compound 202 and/or a thiourea chemical compound206) to form a block copolymer, wherein the intermediate polymer isformed from the polymerizing at 804, and wherein the chemical compoundcan comprise a functional group selected from a group consisting of aurea group and/or a thiourea group. The reacting at 806 can compriseprotonating the urea anion via a proton transfer with the functionalgroup to form an anionic organocatalyst (e.g., another urea anioncatalyst 106), wherein the anionic organocatalyst can be a catalyst tothe second ROP. Additionally, the method 800 can comprise injecting thesecond cyclic monomer and the chemical compound into a stream ofreactants to facilitate the reacting at 806, wherein the chemicalreactants can comprise the intermediate polymer and/or theorganocatalyst.

FIG. 9 illustrates a flow diagram of an example, non-limiting method 900that can facilitate forming one or more polymers (e.g., homopolymersand/or block copolymers) via one or more ROPs within one or more flowreactors 100 using one or more thiourea anion catalysts 108 inaccordance with the one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity.

At 902 the method 900 can comprise selecting one or more organocatalystsfrom a plurality of organocatalysts comprising a thiourea anion based ona reactivity rate of one or more cyclic monomers. For example, the oneor more selected organocatalyst can be thiourea anion catalysts 108.Further, the one or more cyclic monomers can be lactone monomers 102,cyclic carbonate monomers 104, and/or the cyclic monomers depicted inFIG. 2C. For instance, the plurality of organocatalysts (e.g., pluralityof thiourea anion catalysts 108) can be characterized be differingrespective catalytic activities. In other words, a first organocatalyst(e.g., a first thiourea anion catalyst 108) from the plurality oforganocatalysts (e.g., from the plurality of thiourea anion catalysts108) can be more reactive than a second organocatalyst (e.g., a secondthiourea anion catalyst 108) from the plurality of organocatalysts(e.g., from the plurality of thiourea anion catalysts 108). Thus, theselecting at 902 can comprise selecting an organocatalyst (e.g., athiourea anion catalyst 108) with similar reactivity as the subject oneor more cyclic monomers.

At 904, the method 900 can comprise polymerizing, via a ROP within oneor more flow reactors 100, the one or more cyclic monomers in thepresence of the selected one or more organocatalysts comprising thethiourea anion (e.g., the one or more selected thiourea anion catalysts108). For example, the polymerizing at 704 can be performed inaccordance with the second polymerization scheme 120 and/or the fourthpolymerization scheme 126. Further, the one or more selectedorganocatalysts can be one or more of the exemplary thiourea anioncatalysts 108 presented in FIG. 4.

In one or more embodiments (e.g., regarding the polymerization of one ormore block copolymers), the method 900 can further comprise, at 906,reacting, via a second ROP within the flow reactor 100, an intermediatepolymer with a second cyclic monomer (e.g., a lactone monomer 102 and/ora cyclic carbonate monomer 104) in the presence of a chemical compound(e.g., a urea chemical compound 202 and/or a thiourea chemical compound206) to form a block copolymer, wherein the intermediate polymer isformed from the polymerizing at 904, and wherein the chemical compoundcan comprise a functional group selected from a group consisting of aurea group and/or a thiourea group. The reacting at 906 can compriseprotonating the thiourea anion via a proton transfer with the functionalgroup to form an anionic organocatalyst (e.g., another thiourea anioncatalyst 108), wherein the anionic organocatalyst can be a catalyst tothe second ROP. Additionally, the method 900 can comprise injecting thesecond cyclic monomer and the chemical compound into a stream ofreactants to facilitate the reacting at 906, wherein the chemicalreactants can comprise the intermediate polymer and/or theorganocatalyst.

FIG. 10 illustrates a flow diagram of an example, non-limiting method1000 that can facilitate forming one or more polyesters (e.g.,homopolymers and/or block copolymers) via one or more ROPs within one ormore flow reactors 100 using one or more organocatalysts in accordancewith the one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity.

At 1002, the method 1000 can comprise selecting one or moreorganocatalysts from a plurality of organocatalysts comprising based ona reactivity rate of one or more cyclic monomers. For example, the oneor more selected organocatalyst can be urea anion catalysts 106 and/orthiourea anion catalysts 108. Further, the one or more cyclic monomerscan be lactone monomers 102, cyclic carbonate monomers 104, and/or thecyclic monomers depicted in FIG. 2C. Thus, the selecting at 1002 cancomprise selecting an organocatalyst with similar reactivity as thesubject one or more cyclic monomers.

At 1004, the method 1000 can comprise forming one or more polyesters bya ROP of the one or more cyclic monomers in the presence of the selectedorganocatalyst comprising an anion, wherein the ROP can be performedwithin one or more flow reactors 100. As described in variousembodiments herein, the one or more polyesters (e.g., homopolymersand/or copolymers) can be synthesized using a variety of cyclic monomersand/or organocatalysts (e.g., urea anion catalysts 106 and/or thioureaanion catalysts 108).

FIG. 11 illustrates a flow diagram of an example, non-limiting method1100 that can facilitate forming one or more polycarbonates (e.g.,homopolymers and/or block copolymers) via one or more ROPs within one ormore flow reactors 100 using one or more organocatalysts in accordancewith the one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity.

At 1102, the method 1100 can comprise selecting one or moreorganocatalysts from a plurality of organocatalysts comprising based ona reactivity rate of one or more cyclic monomers. For example, the oneor more selected organocatalyst can be urea anion catalysts 106 and/orthiourea anion catalysts 108. Further, the one or more cyclic monomerscan be lactone monomers 102, cyclic carbonate monomers 104, and/or thecyclic monomers depicted in FIG. 2C. Thus, the selecting at 1102 cancomprise selecting an organocatalyst with similar reactivity as thesubject one or more cyclic monomers.

At 1104, the method 1100 can comprise forming one or more polycarbonatesby a ROP of the one or more cyclic monomers in the presences of theselected organocatalyst comprising an anion, wherein the ROP can beperformed within one or more flow reactors 100. As described in variousembodiments herein, the one or more polycarbonates (e.g., homopolymersand/or copolymers) can be synthesized using a variety of cyclic monomersand/or organocatalysts (e.g., urea anion catalysts 106 and/or thioureaanion catalysts 108).

FIG. 12A illustrates a diagram of an example, non-limiting system 1200that can facilitate control (e.g., autonomous control) over one or moreflow reactors 100 to facilitate one or more polymerizations inaccordance with one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity. The system 1200 can comprise oneor more flow reactors 100 operatively coupled to one or more servers1402. The one or more servers 1402 can monitor polymerization conditionswithin the one or more flow reactors 100 and control one or moreparameters of the one or more flow reactors 100. In one or moreembodiments, the system 1200 can be utilized to facilitate one or moreof the chemical reactions described herein (e.g., any of the chemicalreactions described herein) in accordance with one or more embodiments.

In one or more embodiments, the one or more inlets 112 can be connectedto respective compound reservoirs (not shown). The respective compoundreservoirs can contain respective chemical compounds, such as, but notlimited to: one or more lactone monomers 102, one or more cycliccarbonate monomers 104, one or more urea anion catalysts 106, one ormore thiourea anion catalyst 108, one or more chemical bases, one ormore urea chemical compounds 202, one or more thiourea chemicalcompounds 206, a combination thereof, and/or the like. For example, afirst compound reservoir can contain one or more lactone monomers 102and can be connected to a first inlet 112; whereas a second compoundreservoir can contain one or more urea anion catalysts 106 and can beconnected to a second inlet 112. In another example, a first compoundreservoir can contain one or more lactone monomers 102 with a firstchemical structure and can be connected to a first inlet 112; whereas asecond compound reservoir can contain one or more lactone monomers 102with a second chemical structure and can be connected to a second inlet112 While FIG. 12A shows five respective inlets 112, which can beconnected to five respective compound reservoirs, the architecture ofthe one or more flow reactors 100 and/or the system 1200 is not solimited. One of ordinary skill in the art will recognize that the one ormore flow reactors 100 and/or the system 1200 can comprise fewer or moreinlets 112 and/or respective compound reservoirs.

In one or more embodiments, the one or more flow reactors 100 cancomprise one or more controller devices 1204, which can controloperation of one or more respective inlets 112 to manipulate and/orotherwise adjust one or more parameters of the one or more flow reactors100. Example devices that can comprise the one or more controllerdevices 1204 can include, but are not limited to: valves, pumps,actuators, a combination thereof, and/or like. Example parameters thatcan be controlled (e.g., adjusted) by the one or more controller devices1204 can include, but are not limited to: the flow rate at a respectiveinlet 112, whether a respective inlet 112 is open (e.g., therebyenabling one or more chemical compounds contained within a respectivecompound reservoir to flow into the one or more channels 114) or closed(e.g., thereby inhibiting one or more chemical compounds containedwithin a respective compound reservoir from flowing into the one or morechannels 114), how long a respective inlet 112 is open or closed, acombination thereof, and/or the like. In one or more embodiments,operation of the one or more controller devices 1204 can be controlledvia the one or more servers 1202.

The one or more controller devices 1204 can be operatively connected tothe one or more servers 1202 directly and/or indirectly (e.g., asindicated by dashed arrows in FIG. 12A). In one or more embodiments, theone or more controller devices 1204 can be operatively connected to theone or more servers 1202 via one or more networks (e.g., represented bydashed arrows in FIG. 12A).

Additionally, the one or more flow reactors 100 can comprise one or moresensors 1206 that can monitor and/or measure one or more polymerizationconditions within the one or more flow reactors 100. Example sensors1206 can include, but are not limited to: pressure sensors,thermometers, infrared spectrometers, nuclear magnetic resonancespectrometers, a combination thereof, and/or the like. Examplepolymerization conditions that can be monitored by the one or moresensors 1206 can include, but are not limited to: pressure, temperature,monomer conversion, residence time, chemical reactants, a combinationthereof, and/or the like. While FIG. 12A illustrates a flow reactor 100and/or system 1200 comprising two sensors 1206, the architecture of theone or more flow reactors 100 and/or system 1200 is not so limited. Forexample, the one or more flow reactors 100 and/or the system 1200 cancomprise fewer or more sensors 1206 than the two depicted in FIG. 12A.Further, the one or more sensors 1206 can be positioned at variouslocations throughout the flow reactor 100 and/or the system 1200. In oneor more embodiments, one or more of the sensors 1206 can be positionedoutside the one or more flow reactors 100 and can monitor and/or measureone or more characteristics of polymers synthesized via the one or moreflow reactors 100. Additionally, the one or more sensors 1206 can bepositioned within and/or outside the one or channels 114 of the one ormore flow reactors 100.

The one or more sensors 1206 can be operatively coupled to the one ormore servers 1202 directly and/or indirectly (e.g., as indicated bydashed arrows in FIG. 12A). In one or more embodiments, the one or morecontroller devices 1204 can be operatively connected to the one or moreservers 1202 via one or more networks (e.g., represented by dashedarrows in FIG. 12A).

The one or more networks (e.g., represented by dashed lines in FIG. 12A)that can operatively couple the one or more controller devices 1204and/or the one or more sensors 1206 to the one or more servers 1202 cancomprise wired and wireless networks, including, but not limited to, acellular network, a wide area network (WAN) (e.g., the Internet) or alocal area network (LAN). For example, the server 1202 can communicatewith the one or more one or more controller devices 1204 and/or one ormore sensors 1206 (and vice versa) using virtually any desired wired orwireless technology including for example, but not limited to: cellular,WAN, wireless fidelity (Wi-Fi), Wi-Max, WLAN, Bluetooth technology, acombination thereof, and/or the like.

In various embodiments, one or more aspects of the one or more servers1202 can constitute one or more machine-executable components embodiedwithin one or more machines, e.g., embodied in one or more computerreadable mediums (or media) associated with one or more machines. Suchcomponents, when executed by the one or more machines, e.g., computers,computing devices, virtual machines, etc. can cause the machines toperform the operations described. The one or more servers 1202 cancomprise analysis component 1208. In one or more embodiments, the server1202 can be located in and/or other communicate with a cloud computingenvironment. The one or more servers 1202 can receive data from the oneor more sensors 1206 regarding monitored and/or measured polymerconditions and send one or more commands to the one or more controllerdevices 1204 to control and/or otherwise adjust one or more parametersof the one or more flow reactors 100.

In one or more embodiments the analysis component 1208 can determineoptimal polymerization conditions to synthesize one or more targetpolymers by: controlling the one or more controller devices 1204 toconduct a plurality of variations to a subject polymerization;controlling the one or more controller devices 1204 to facilitatedifferent flow reactor 100 parameters for each respective variation;and/or monitoring the resulting polymerization conditions associatedwith each variation. For example, to determine an optimal flow rate fora given ROP in the one or more flow reactor 100, the analysis component1208 can control the one or more flow reactors 100 (e.g., via operationof the one or more controller devices 1204) to conduct multipleiterations of the ROP, each iteration with a different flow rate. Theanalysis component 1208 can than compare one or more polymerizationconditions (e.g., molecular weight distribution) associated with eachiteration (e.g., by the one or more sensors 1206) to identify theiteration associated with the most preferred polymerization conditionand thereby determine the optimal flow rate.

In another example, the analysis component 1208 can control the one ormore controller devices 1204 to change the identity of a catalyst usedin a subject ROP within the one or more flow reactor 100. The analysiscomponent 1208 can perform multiple iterations of the ROP, wherein ineach respective iteration a different inlet 112 is opened and/or closedby the one or more controller devices 1204 to facilitate theintroduction of a different catalyst (e.g., a urea anion catalyst 106and/or a thiourea anion catalyst 108). The analysis component 1208 canthan compare one or more polymerization conditions (e.g., molecularweight distribution) associated with each iteration (e.g., by the one ormore sensors 1206) to identify the iteration associated with the mostpreferred polymerization condition and thereby determine the optimalcatalyst.

Further, for iterations of a given polymerization, the analysiscomponent 1208 can store the detected polymerization conditions and/orassociate flow reactor 100 parameters in a computer memory. Forinstance, the analysis component 1208 can control the one or more flowreactors 100 to collect the data comprised within, for example, Tables1-4. Additionally, the one or more servers 1202 can share data regardingpolymerization conditions (e.g., as monitored and/or detected by the oneor more sensors 1206) and/or associate flow reactor 100 parameters(e.g., operational conditions of one or more inlets 112) with one ormore other servers 1202 (e.g., to facilitate optimization of one or morepolymerization conditions in one or more other flow reactors 100).

In one or more embodiments, the one or more servers 1202 act as anInternet of Thinks (“IoT”) interface between the system 1200 and one ormore artificial intelligence technologies (“AI”) and/or user drivenprogram platforms to facilitate cognitively designed flow reactor 100parameters that can optimize target polymerization conditions for agiven polymerization. For example, the one or more AI technologies canutilize one or more optimization methods (e.g., differential evolutionand/or effective differential evolution algorithms) to analyze datacollected by one or more servers 1202 regarding one or morepolymerization variations.

FIG. 12B illustrates a diagram of the example, non-limiting system 1200that can facilitate control (e.g., autonomous control) over one or moreflow reactors 100 to facilitate one or more polymerizations inaccordance with one or more embodiments described herein. Repetitivedescription of like elements employed in other embodiments describedherein is omitted for sake of brevity. FIG. 12B exemplifies that thesystem 1200 is not limited to use of a single flow reactor 100, a singleset of reactor loops 116, and/or a single polymerization (e.g., ROP).For example, as shown in FIG. 12B the system 1200 can be utilized tocontrol and/or analyze one or more flow reactors 100 for synthesesinvolving multiple ROPs, such as the one or more polymerization schemesdepicted and/or described with regards to FIGS. 1-11B.

It is to be understood that although this disclosure includes a detaileddescription on cloud computing, implementation of the teachings recitedherein are not limited to a cloud computing environment. Rather,embodiments of the present invention are capable of being implemented inconjunction with any other type of computing environment now known orlater developed.

Cloud computing is a model of service delivery for enabling convenient,on-demand network access to a shared pool of configurable computingresources (e.g., networks, network bandwidth, servers, processing,memory, storage, applications, virtual machines, and services) that canbe rapidly provisioned and released with minimal management effort orinteraction with a provider of the service. This cloud model may includeat least five characteristics, at least three service models, and atleast four deployment models.

Characteristics are as follows:

On-demand self-service: a cloud consumer can unilaterally provisioncomputing capabilities, such as server time and network storage, asneeded automatically without requiring human interaction with theservice's provider.

Broad network access: capabilities are available over a network andaccessed through standard mechanisms that promote use by heterogeneousthin or thick client platforms (e.g., mobile phones, laptops, and PDAs).

Resource pooling: the provider's computing resources are pooled to servemultiple consumers using a multi-tenant model, with different physicaland virtual resources dynamically assigned and reassigned according todemand. There is a sense of location independence in that the consumergenerally has no control or knowledge over the exact location of theprovided resources but may be able to specify location at a higher levelof abstraction (e.g., country, state, or datacenter).

Rapid elasticity: capabilities can be rapidly and elasticallyprovisioned, in some cases automatically, to quickly scale out andrapidly released to quickly scale in. To the consumer, the capabilitiesavailable for provisioning often appear to be unlimited and can bepurchased in any quantity at any time.

Measured service: cloud systems automatically control and optimizeresource use by leveraging a metering capability at some level ofabstraction appropriate to the type of service (e.g., storage,processing, bandwidth, and active user accounts). Resource usage can bemonitored, controlled, and reported, providing transparency for both theprovider and consumer of the utilized service.

Service Models are as follows:

Software as a Service (SaaS): the capability provided to the consumer isto use the provider's applications running on a cloud infrastructure.The applications are accessible from various client devices through athin client interface such as a web browser (e.g., web-based e-mail).The consumer does not manage or control the underlying cloudinfrastructure including network, servers, operating systems, storage,or even individual application capabilities, with the possible exceptionof limited user-specific application configuration settings.

Platform as a Service (PaaS): the capability provided to the consumer isto deploy onto the cloud infrastructure consumer-created or acquiredapplications created using programming languages and tools supported bythe provider. The consumer does not manage or control the underlyingcloud infrastructure including networks, servers, operating systems, orstorage, but has control over the deployed applications and possiblyapplication hosting environment configurations.

Infrastructure as a Service (IaaS): the capability provided to theconsumer is to provision processing, storage, networks, and otherfundamental computing resources where the consumer is able to deploy andrun arbitrary software, which can include operating systems andapplications. The consumer does not manage or control the underlyingcloud infrastructure but has control over operating systems, storage,deployed applications, and possibly limited control of select networkingcomponents (e.g., host firewalls).

Deployment Models are as follows:

Private cloud: the cloud infrastructure is operated solely for anorganization. It may be managed by the organization or a third party andmay exist on-premises or off-premises.

Community cloud: the cloud infrastructure is shared by severalorganizations and supports a specific community that has shared concerns(e.g., mission, security requirements, policy, and complianceconsiderations). It may be managed by the organizations or a third partyand may exist on-premises or off-premises.

Public cloud: the cloud infrastructure is made available to the generalpublic or a large industry group and is owned by an organization sellingcloud services.

Hybrid cloud: the cloud infrastructure is a composition of two or moreclouds (private, community, or public) that remain unique entities butare bound together by standardized or proprietary technology thatenables data and application portability (e.g., cloud bursting forload-balancing between clouds).

A cloud computing environment is service oriented with a focus onstatelessness, low coupling, modularity, and semantic interoperability.At the heart of cloud computing is an infrastructure that includes anetwork of interconnected nodes.

Referring now to FIG. 13, illustrative cloud computing environment 1300is depicted. Repetitive description of like elements employed in otherembodiments described herein is omitted for sake of brevity. As shown,cloud computing environment 1300 includes one or more cloud computingnodes 1302 with which local computing devices used by cloud consumers,such as, for example, personal digital assistant (PDA) or cellulartelephone 1304, desktop computer 1306, laptop computer 1308, and/orautomobile computer system 1310 may communicate. Nodes 1302 maycommunicate with one another. They may be grouped (not shown) physicallyor virtually, in one or more networks, such as Private, Community,Public, or Hybrid clouds as described hereinabove, or a combinationthereof. This allows cloud computing environment 1300 to offerinfrastructure, platforms and/or software as services for which a cloudconsumer does not need to maintain resources on a local computingdevice. It is understood that the types of computing devices 1304-1310shown in FIG. 13 are intended to be illustrative only and that computingnodes 1302 and cloud computing environment 1300 can communicate with anytype of computerized device over any type of network and/or networkaddressable connection (e.g., using a web browser).

Referring now to FIG. 14, a set of functional abstraction layersprovided by cloud computing environment 1300 (FIG. 13) is shown.Repetitive description of like elements employed in other embodimentsdescribed herein is omitted for sake of brevity. It should be understoodin advance that the components, layers, and functions shown in FIG. 14are intended to be illustrative only and embodiments of the inventionare not limited thereto. As depicted, the following layers andcorresponding functions are provided.

Hardware and software layer 1402 includes hardware and softwarecomponents. Examples of hardware components include: mainframes 1404;RISC (Reduced Instruction Set Computer) architecture based servers 1406;servers 1408; blade servers 1410; storage devices 141412; and networksand networking components 1414. In some embodiments, software componentsinclude network application server software 1416 and database software1418.

Virtualization layer 1420 provides an abstraction layer from which thefollowing examples of virtual entities may be provided: virtual servers1422; virtual storage 1424; virtual networks 1426, including virtualprivate networks; virtual applications and operating systems 1428; andvirtual clients 1430.

In one example, management layer 1432 may provide the functionsdescribed below. Resource provisioning 1434 provides dynamic procurementof computing resources and other resources that are utilized to performtasks within the cloud computing environment. Metering and Pricing 1436provide cost tracking as resources are utilized within the cloudcomputing environment, and billing or invoicing for consumption of theseresources. In one example, these resources may include applicationsoftware licenses. Security provides identity verification for cloudconsumers and tasks, as well as protection for data and other resources.User portal 1438 provides access to the cloud computing environment forconsumers and system administrators. Service level management 1440provides cloud computing resource allocation and management such thatrequired service levels are met. Service Level Agreement (SLA) planningand fulfillment 1442 provide pre-arrangement for, and procurement of,cloud computing resources for which a future requirement is anticipatedin accordance with an SLA.

Workloads layer 1444 provides examples of functionality for which thecloud computing environment may be utilized. Examples of workloads andfunctions which may be provided from this layer include: mapping andnavigation 1446; software development and lifecycle management 1448;virtual classroom education delivery 1450; data analytics processing1452; transaction processing 1454; and/or polymerization design 1456.Various embodiments of the present invention can utilize the cloudcomputing environment described with reference to FIGS. 13 and 14 tofacilitate optimizing one or more polymerization conditions viamanipulation and/or control of one or more parameters of one or moreflow reactors 100.

The present invention may be a system, a method, and/or a computerprogram product at any possible technical detail level of integration.The computer program product may include a computer readable storagemedium (or media) having computer readable program instructions thereonfor causing a processor to carry out aspects of the present invention.The computer readable storage medium can be a tangible device that canretain and store instructions for use by an instruction executiondevice. The computer readable storage medium may be, for example, but isnot limited to, an electronic storage device, a magnetic storage device,an optical storage device, an electromagnetic storage device, asemiconductor storage device, or any suitable combination of theforegoing.

A non-exhaustive list of more specific examples of the computer readablestorage medium includes the following: a portable computer diskette, ahard disk, a random access memory (RAM), a read-only memory (ROM), anerasable programmable read-only memory (EPROM or Flash memory), a staticrandom access memory (SRAM), a portable compact disc read-only memory(CD-ROM), a digital versatile disk (DVD), a memory stick, a floppy disk,a mechanically encoded device such as punch-cards or raised structuresin a groove having instructions recorded thereon, and any suitablecombination of the foregoing. A computer readable storage medium, asused herein, is not to be construed as being transitory signals per se,such as radio waves or other freely propagating electromagnetic waves,electromagnetic waves propagating through a waveguide or othertransmission media (e.g., light pulses passing through a fiber-opticcable), or electrical signals transmitted through a wire.

Computer readable program instructions described herein can bedownloaded to respective computing/processing devices from a computerreadable storage medium or to an external computer or external storagedevice via a network, for example, the Internet, a local area network, awide area network and/or a wireless network. The network may comprisecopper transmission cables, optical transmission fibers, wirelesstransmission, routers, firewalls, switches, gateway computers and/oredge servers. A network adapter card or network interface in eachcomputing/processing device receives computer readable programinstructions from the network and forwards the computer readable programinstructions for storage in a computer readable storage medium withinthe respective computing/processing device.

Computer readable program instructions for carrying out operations ofthe present invention may be assembler instructions,instruction-set-architecture (ISA) instructions, machine instructions,machine dependent instructions, microcode, firmware instructions,state-setting data, configuration data for integrated circuitry, oreither source code or object code written in any combination of one ormore programming languages, including an object oriented programminglanguage such as Smalltalk, C++, or the like, and procedural programminglanguages, such as the “C” programming language or similar programminglanguages. The computer readable program instructions may executeentirely on the user's computer, partly on the user's computer, as astand-alone software package, partly on the user's computer and partlyon a remote computer or entirely on the remote computer or server. Inthe latter scenario, the remote computer may be connected to the user'scomputer through any type of network, including a local area network(LAN) or a wide area network (WAN), or the connection may be made to anexternal computer (for example, through the Internet using an InternetService Provider). In some embodiments, electronic circuitry including,for example, programmable logic circuitry, field-programmable gatearrays (FPGA), or programmable logic arrays (PLA) may execute thecomputer readable program instructions by utilizing state information ofthe computer readable program instructions to personalize the electroniccircuitry, in order to perform aspects of the present invention.

Aspects of the present invention are described herein with reference toflowchart illustrations and/or block diagrams of methods, apparatus(systems), and computer program products according to embodiments of theinvention. It will be understood that each block of the flowchartillustrations and/or block diagrams, and combinations of blocks in theflowchart illustrations and/or block diagrams, can be implemented bycomputer readable program instructions.

These computer readable program instructions may be provided to aprocessor of a general purpose computer, special purpose computer, orother programmable data processing apparatus to produce a machine, suchthat the instructions, which execute via the processor of the computeror other programmable data processing apparatus, create means forimplementing the functions/acts specified in the flowchart and/or blockdiagram block or blocks. These computer readable program instructionsmay also be stored in a computer readable storage medium that can directa computer, a programmable data processing apparatus, and/or otherdevices to function in a particular manner, such that the computerreadable storage medium having instructions stored therein comprises anarticle of manufacture including instructions which implement aspects ofthe function/act specified in the flowchart and/or block diagram blockor blocks.

The computer readable program instructions may also be loaded onto acomputer, other programmable data processing apparatus, or other deviceto cause a series of operational steps to be performed on the computer,other programmable apparatus or other device to produce a computerimplemented process, such that the instructions which execute on thecomputer, other programmable apparatus, or other device implement thefunctions/acts specified in the flowchart and/or block diagram block orblocks.

The flowchart and block diagrams in the Figures illustrate thearchitecture, functionality, and operation of possible implementationsof systems, methods, and computer program products according to variousembodiments of the present invention. In this regard, each block in theflowchart or block diagrams may represent a module, segment, or portionof instructions, which comprises one or more executable instructions forimplementing the specified logical function(s). In some alternativeimplementations, the functions noted in the blocks may occur out of theorder noted in the Figures. For example, two blocks shown in successionmay, in fact, be executed substantially concurrently, or the blocks maysometimes be executed in the reverse order, depending upon thefunctionality involved. It will also be noted that each block of theblock diagrams and/or flowchart illustration, and combinations of blocksin the block diagrams and/or flowchart illustration, can be implementedby special purpose hardware based systems that perform the specifiedfunctions or acts or carry out combinations of special purpose hardwareand computer instructions.

In order to provide a context for the various aspects of the disclosedsubject matter, FIG. 15 as well as the following discussion are intendedto provide a general description of a suitable environment in which thevarious aspects of the disclosed subject matter, such as the one or moreservers 1202, can be implemented. FIG. 15 illustrates a block diagram ofan example, non-limiting operating environment in which one or moreembodiments described herein can be facilitated. Repetitive descriptionof like elements employed in other embodiments described herein isomitted for sake of brevity. With reference to FIG. 15, a suitableoperating environment 1500 for implementing various aspects of thisdisclosure can include a computer 1512. The computer 1512 can alsoinclude a processing unit 1514, a system memory 1516, and a system bus1518. The system bus 1518 can operably couple system componentsincluding, but not limited to, the system memory 1516 to the processingunit 1514. The processing unit 1514 can be any of various availableprocessors. Dual microprocessors and other multiprocessor architecturesalso can be employed as the processing unit 1514. The system bus 1518can be any of several types of bus structures including the memory busor memory controller, a peripheral bus or external bus, and/or a localbus using any variety of available bus architectures including, but notlimited to, Industrial Standard Architecture (ISA), Micro-ChannelArchitecture (MSA), Extended ISA (EISA), Intelligent Drive Electronics(IDE), VESA Local Bus (VLB), Peripheral Component Interconnect (PCI),Card Bus, Universal Serial Bus (USB), Advanced Graphics Port (AGP),Firewire, and Small Computer Systems Interface (SCSI). The system memory1516 can also include volatile memory 1520 and nonvolatile memory 1522.The basic input/output system (BIOS), containing the basic routines totransfer information between elements within the computer 1512, such asduring start-up, can be stored in nonvolatile memory 1522. By way ofillustration, and not limitation, nonvolatile memory 1522 can includeread only memory (ROM), programmable ROM (PROM), electricallyprogrammable ROM (EPROM), electrically erasable programmable ROM(EEPROM), flash memory, or nonvolatile random access memory (RAM) (e.g.,ferroelectric RAM (FeRAM). Volatile memory 1520 can also include randomaccess memory (RAM), which acts as external cache memory. By way ofillustration and not limitation, RAM is available in many forms such asstatic RAM (SRAM), dynamic RAM (DRAM), synchronous DRAM (SDRAM), doubledata rate SDRAM (DDR SDRAM), enhanced SDRAM (ESDRAM), Synchlink DRAM(SLDRAM), direct Rambus RAM (DRRAM), direct Rambus dynamic RAM (DRDRAM),and Rambus dynamic RAM.

Computer 1512 can also include removable/non-removable,volatile/non-volatile computer storage media. FIG. 15 illustrates, forexample, a disk storage 1524. Disk storage 1524 can also include, but isnot limited to, devices like a magnetic disk drive, floppy disk drive,tape drive, Jaz drive, Zip drive, LS-100 drive, flash memory card, ormemory stick. The disk storage 1524 also can include storage mediaseparately or in combination with other storage media including, but notlimited to, an optical disk drive such as a compact disk ROM device(CD-ROM), CD recordable drive (CD-R Drive), CD rewritable drive (CD-RWDrive) or a digital versatile disk ROM drive (DVD-ROM). To facilitateconnection of the disk storage 1524 to the system bus 1518, a removableor non-removable interface can be used, such as interface 1526. FIG. 15also depicts software that can act as an intermediary between users andthe basic computer resources described in the suitable operatingenvironment 1500. Such software can also include, for example, anoperating system 1528. Operating system 1528, which can be stored ondisk storage 1524, acts to control and allocate resources of thecomputer 1512. System applications 1530 can take advantage of themanagement of resources by operating system 1528 through program modules1532 and program data 1534, e.g., stored either in system memory 1516 oron disk storage 1524. It is to be appreciated that this disclosure canbe implemented with various operating systems or combinations ofoperating systems. A user enters commands or information into thecomputer 1512 through one or more input devices 1536. Input devices 1536can include, but are not limited to, a pointing device such as a mouse,trackball, stylus, touch pad, keyboard, microphone, joystick, game pad,satellite dish, scanner, TV tuner card, digital camera, digital videocamera, web camera, and the like. These and other input devices canconnect to the processing unit 1514 through the system bus 1518 via oneor more interface ports 1538. The one or more Interface ports 1538 caninclude, for example, a serial port, a parallel port, a game port, and auniversal serial bus (USB). One or more output devices 1540 can use someof the same type of ports as input device 1536. Thus, for example, a USBport can be used to provide input to computer 1512, and to outputinformation from computer 1512 to an output device 1540. Output adapter1542 can be provided to illustrate that there are some output devices1540 like monitors, speakers, and printers, among other output devices1540, which require special adapters. The output adapters 1542 caninclude, by way of illustration and not limitation, video and soundcards that provide a means of connection between the output device 1540and the system bus 1518. It should be noted that other devices and/orsystems of devices provide both input and output capabilities such asone or more remote computers 1544.

Computer 1512 can operate in a networked environment using logicalconnections to one or more remote computers, such as remote computer1544. The remote computer 1544 can be a computer, a server, a router, anetwork PC, a workstation, a microprocessor based appliance, a peerdevice or other common network node and the like, and typically can alsoinclude many or all of the elements described relative to computer 1512.For purposes of brevity, only a memory storage device 1546 isillustrated with remote computer 1544. Remote computer 1544 can belogically connected to computer 1512 through a network interface 1548and then physically connected via communication connection 1550.Further, operation can be distributed across multiple (local and remote)systems. Network interface 1548 can encompass wire and/or wirelesscommunication networks such as local-area networks (LAN), wide-areanetworks (WAN), cellular networks, etc. LAN technologies include FiberDistributed Data Interface (FDDI), Copper Distributed Data Interface(CDDI), Ethernet, Token Ring and the like. WAN technologies include, butare not limited to, point-to-point links, circuit switching networkslike Integrated Services Digital Networks (ISDN) and variations thereon,packet switching networks, and Digital Subscriber Lines (DSL). One ormore communication connections 1550 refers to the hardware/softwareemployed to connect the network interface 1548 to the system bus 1518.While communication connection 1550 is shown for illustrative clarityinside computer 1512, it can also be external to computer 1512. Thehardware/software for connection to the network interface 1548 can alsoinclude, for exemplary purposes only, internal and external technologiessuch as, modems including regular telephone grade modems, cable modemsand DSL modems, ISDN adapters, and Ethernet cards.

Embodiments of the present invention can be a system, a method, anapparatus and/or a computer program product at any possible technicaldetail level of integration. The computer program product can include acomputer readable storage medium (or media) having computer readableprogram instructions thereon for causing a processor to carry outaspects of the present invention. The computer readable storage mediumcan be a tangible device that can retain and store instructions for useby an instruction execution device. The computer readable storage mediumcan be, for example, but is not limited to, an electronic storagedevice, a magnetic storage device, an optical storage device, anelectromagnetic storage device, a semiconductor storage device, or anysuitable combination of the foregoing. A non-exhaustive list of morespecific examples of the computer readable storage medium can alsoinclude the following: a portable computer diskette, a hard disk, arandom access memory (RAM), a read-only memory (ROM), an erasableprogrammable read-only memory (EPROM or Flash memory), a static randomaccess memory (SRAM), a portable compact disc read-only memory (CD-ROM),a digital versatile disk (DVD), a memory stick, a floppy disk, amechanically encoded device such as punch-cards or raised structures ina groove having instructions recorded thereon, and any suitablecombination of the foregoing. A computer readable storage medium, asused herein, is not to be construed as being transitory signals per se,such as radio waves or other freely propagating electromagnetic waves,electromagnetic waves propagating through a waveguide or othertransmission media (e.g., light pulses passing through a fiber-opticcable), or electrical signals transmitted through a wire.

Computer readable program instructions described herein can bedownloaded to respective computing/processing devices from a computerreadable storage medium or to an external computer or external storagedevice via a network, for example, the Internet, a local area network, awide area network and/or a wireless network. The network can includecopper transmission cables, optical transmission fibers, wirelesstransmission, routers, firewalls, switches, gateway computers and/oredge servers. A network adapter card or network interface in eachcomputing/processing device receives computer readable programinstructions from the network and forwards the computer readable programinstructions for storage in a computer readable storage medium withinthe respective computing/processing device. Computer readable programinstructions for carrying out operations of various aspects of thepresent invention can be assembler instructions,instruction-set-architecture (ISA) instructions, machine instructions,machine dependent instructions, microcode, firmware instructions,state-setting data, configuration data for integrated circuitry, oreither source code or object code written in any combination of one ormore programming languages, including an object oriented programminglanguage such as Smalltalk, C++, or the like, and procedural programminglanguages, such as the “C” programming language or similar programminglanguages. The computer readable program instructions can executeentirely on the user's computer, partly on the user's computer, as astand-alone software package, partly on the user's computer and partlyon a remote computer or entirely on the remote computer or server. Inthe latter scenario, the remote computer can be connected to the user'scomputer through any type of network, including a local area network(LAN) or a wide area network (WAN), or the connection can be made to anexternal computer (for example, through the Internet using an InternetService Provider). In some embodiments, electronic circuitry including,for example, programmable logic circuitry, field-programmable gatearrays (FPGA), or programmable logic arrays (PLA) can execute thecomputer readable program instructions by utilizing state information ofthe computer readable program instructions to customize the electroniccircuitry, in order to perform aspects of the present invention.

Aspects of the present invention are described herein with reference toflowchart illustrations and/or block diagrams of methods, apparatus(systems), and computer program products according to embodiments of theinvention. It will be understood that each block of the flowchartillustrations and/or block diagrams, and combinations of blocks in theflowchart illustrations and/or block diagrams, can be implemented bycomputer readable program instructions. These computer readable programinstructions can be provided to a processor of a general purposecomputer, special purpose computer, or other programmable dataprocessing apparatus to produce a machine, such that the instructions,which execute via the processor of the computer or other programmabledata processing apparatus, create means for implementing thefunctions/acts specified in the flowchart and/or block diagram block orblocks. These computer readable program instructions can also be storedin a computer readable storage medium that can direct a computer, aprogrammable data processing apparatus, and/or other devices to functionin a particular manner, such that the computer readable storage mediumhaving instructions stored therein includes an article of manufactureincluding instructions which implement aspects of the function/actspecified in the flowchart and/or block diagram block or blocks. Thecomputer readable program instructions can also be loaded onto acomputer, other programmable data processing apparatus, or other deviceto cause a series of operational acts to be performed on the computer,other programmable apparatus or other device to produce a computerimplemented process, such that the instructions which execute on thecomputer, other programmable apparatus, or other device implement thefunctions/acts specified in the flowchart and/or block diagram block orblocks.

The flowchart and block diagrams in the Figures illustrate thearchitecture, functionality, and operation of possible implementationsof systems, methods, and computer program products according to variousembodiments of the present invention. In this regard, each block in theflowchart or block diagrams can represent a module, segment, or portionof instructions, which includes one or more executable instructions forimplementing the specified logical function(s). In some alternativeimplementations, the functions noted in the blocks can occur out of theorder noted in the Figures. For example, two blocks shown in successioncan, in fact, be executed substantially concurrently, or the blocks cansometimes be executed in the reverse order, depending upon thefunctionality involved. It will also be noted that each block of theblock diagrams and/or flowchart illustration, and combinations of blocksin the block diagrams and/or flowchart illustration, can be implementedby special purpose hardware-based systems that perform the specifiedfunctions or acts or carry out combinations of special purpose hardwareand computer instructions.

While the subject matter has been described above in the general contextof computer-executable instructions of a computer program product thatruns on a computer and/or computers, those skilled in the art willrecognize that this disclosure also can or can be implemented incombination with other program modules. Generally, program modulesinclude routines, programs, components, data structures, etc. thatperform particular tasks and/or implement particular abstract datatypes. Moreover, those skilled in the art will appreciate that theinventive computer-implemented methods can be practiced with othercomputer system configurations, including single-processor ormultiprocessor computer systems, mini-computing devices, mainframecomputers, as well as computers, hand-held computing devices (e.g., PDA,phone), microprocessor-based or programmable consumer or industrialelectronics, and the like. The illustrated aspects can also be practicedin distributed computing environments where tasks are performed byremote processing devices that are linked through a communicationsnetwork. However, some, if not all aspects of this disclosure can bepracticed on stand-alone computers. In a distributed computingenvironment, program modules can be located in both local and remotememory storage devices.

As used in this application, the terms “component,” “system,”“platform,” “interface,” and the like, can refer to and/or can include acomputer-related entity or an entity related to an operational machinewith one or more specific functionalities. The entities disclosed hereincan be either hardware, a combination of hardware and software,software, or software in execution. For example, a component can be, butis not limited to being, a process running on a processor, a processor,an object, an executable, a thread of execution, a program, and/or acomputer. By way of illustration, both an application running on aserver and the server can be a component. One or more components canreside within a process and/or thread of execution and a component canbe localized on one computer and/or distributed between two or morecomputers. In another example, respective components can execute fromvarious computer readable media having various data structures storedthereon. The components can communicate via local and/or remoteprocesses such as in accordance with a signal having one or more datapackets (e.g., data from one component interacting with anothercomponent in a local system, distributed system, and/or across a networksuch as the Internet with other systems via the signal). As anotherexample, a component can be an apparatus with specific functionalityprovided by mechanical parts operated by electric or electroniccircuitry, which is operated by a software or firmware applicationexecuted by a processor. In such a case, the processor can be internalor external to the apparatus and can execute at least a part of thesoftware or firmware application. As yet another example, a componentcan be an apparatus that provides specific functionality throughelectronic components without mechanical parts, wherein the electroniccomponents can include a processor or other means to execute software orfirmware that confers at least in part the functionality of theelectronic components. In an aspect, a component can emulate anelectronic component via a virtual machine, e.g., within a cloudcomputing system.

In addition, the term “or” is intended to mean an inclusive “or” ratherthan an exclusive “or.” That is, unless specified otherwise, or clearfrom context, “X employs A or B” is intended to mean any of the naturalinclusive permutations. That is, if X employs A; X employs B; or Xemploys both A and B, then “X employs A or B” is satisfied under any ofthe foregoing instances. Moreover, articles “a” and “an” as used in thesubject specification and annexed drawings should generally be construedto mean “one or more” unless specified otherwise or clear from contextto be directed to a singular form. As used herein, the terms “example”and/or “exemplary” are utilized to mean serving as an example, instance,or illustration. For the avoidance of doubt, the subject matterdisclosed herein is not limited by such examples. In addition, anyaspect or design described herein as an “example” and/or “exemplary” isnot necessarily to be construed as preferred or advantageous over otheraspects or designs, nor is it meant to preclude equivalent exemplarystructures and techniques known to those of ordinary skill in the art.

As it is employed in the subject specification, the term “processor” canrefer to substantially any computing processing unit or deviceincluding, but not limited to, single-core processors; single-processorswith software multithread execution capability; multi-core processors;multi-core processors with software multithread execution capability;multi-core processors with hardware multithread technology; parallelplatforms; and parallel platforms with distributed shared memory.Additionally, a processor can refer to an integrated circuit, anapplication specific integrated circuit (ASIC), a digital signalprocessor (DSP), a field programmable gate array (FPGA), a programmablelogic controller (PLC), a complex programmable logic device (CPLD), adiscrete gate or transistor logic, discrete hardware components, or anycombination thereof designed to perform the functions described herein.Further, processors can exploit nano-scale architectures such as, butnot limited to, molecular and quantum-dot based transistors, switchesand gates, in order to optimize space usage or enhance performance ofuser equipment. A processor can also be implemented as a combination ofcomputing processing units. In this disclosure, terms such as “store,”“storage,” “data store,” data storage,” “database,” and substantiallyany other information storage component relevant to operation andfunctionality of a component are utilized to refer to “memorycomponents,” entities embodied in a “memory,” or components including amemory. It is to be appreciated that memory and/or memory componentsdescribed herein can be either volatile memory or nonvolatile memory, orcan include both volatile and nonvolatile memory. By way ofillustration, and not limitation, nonvolatile memory can include readonly memory (ROM), programmable ROM (PROM), electrically programmableROM (EPROM), electrically erasable ROM (EEPROM), flash memory, ornonvolatile random access memory (RAM) (e.g., ferroelectric RAM (FeRAM).Volatile memory can include RAM, which can act as external cache memory,for example. By way of illustration and not limitation, RAM is availablein many forms such as synchronous RAM (SRAM), dynamic RAM (DRAM),synchronous DRAM (SDRAM), double data rate SDRAM (DDR SDRAM), enhancedSDRAM (ESDRAM), Synchlink DRAM (SLDRAM), direct Rambus RAM (DRRAM),direct Rambus dynamic RAM (DRDRAM), and Rambus dynamic RAM (RDRAM).Additionally, the disclosed memory components of systems orcomputer-implemented methods herein are intended to include, withoutbeing limited to including, these and any other suitable types ofmemory.

What has been described above include mere examples of systems, computerprogram products and computer-implemented methods. It is, of course, notpossible to describe every conceivable combination of components,products and/or computer-implemented methods for purposes of describingthis disclosure, but one of ordinary skill in the art can recognize thatmany further combinations and permutations of this disclosure arepossible. Furthermore, to the extent that the terms “includes,” “has,”“possesses,” and the like are used in the detailed description, claims,appendices and drawings such terms are intended to be inclusive in amanner similar to the term “comprising” as “comprising” is interpretedwhen employed as a transitional word in a claim. The descriptions of thevarious embodiments have been presented for purposes of illustration,but are not intended to be exhaustive or limited to the embodimentsdisclosed. Many modifications and variations will be apparent to thoseof ordinary skill in the art without departing from the scope and spiritof the described embodiments. The terminology used herein was chosen tobest explain the principles of the embodiments, the practicalapplication or technical improvement over technologies found in themarketplace, or to enable others of ordinary skill in the art tounderstand the embodiments disclosed herein.

What is claimed is:
 1. A method, comprising: polymerizing, via aring-opening polymerization within a flow reactor, a cyclic monomer inthe presence of an organocatalyst comprising a thiourea anion tosynthesize a homopolymer, wherein the ring-opening polymerization has aresidence time within the flow reactor of greater than or equal to 0.006seconds and less than or equal to 3.5 seconds.
 2. The method of claim 1,wherein the cyclic monomer is selected from a group consisting of alactone monomer, a cyclic carbonate monomer, a substituted cycliccarbonate monomer, a cyclic phospholane monomer, a morpholinone monomer,tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone,and 2-thiepanone.
 3. The method of claim 2, wherein the organocatalystis derived from a chemical compound selected from a second groupconsisting of N,N′-di[3,5-di(trifluoromethyl)phenyl]thiourea,1-[3,5-bis(trifluoromethyl)phenyl]-3-[3-(trifluoromethyl)phenyl]thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylthiourea,1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea,1-phenyl-3-[3-(trifluoromethyl)phenyl] thiourea, N,N′-diphenylthiourea,and 1-cyclohexyl-3-phenylthiourea.
 4. The method of claim 3, wherein thethiourea anion is derived from a chemical reaction between the chemicalcompound and a chemical base, wherein the chemical base is selected froma third group consisting of 1,8-diazabicyclo[5.4.0[undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, phosphazene bases,1,3,2-diazaphosphorin-2-amin,2-[(1,1-dimethylethyl)imino]-N,N-diethyl-1,2,2,2,3,4,5,6-octahydro-1,3-dimethyl,1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, potassiummethoxide, potassium hydride, sodium methoxide, and sodium hydride. 5.The method of claim 1, further comprising: selecting the organocatalystfrom a plurality of organocatalysts comprising the thiourea anion basedon a reactivity rate of the cyclic monomer.
 6. The method of claim 1,further comprising: reacting, via a second ring-opening polymerizationwithin the flow reactor, an intermediate polymer with a second cyclicmonomer in the presence of a chemical compound to form a blockcopolymer, wherein the intermediate polymer is formed from thepolymerizing the cyclic monomer, and wherein the chemical compoundcomprises a functional group selected from a thiourea group.
 7. Themethod of claim 6, wherein the reacting comprises protonating thethiourea anion via a proton transfer with the functional group to forman anionic organocatalyst, and wherein the anionic organocatalyst is acatalyst to the second ring-opening polymerization.
 8. The method ofclaim 7, further comprising injecting the second cyclic monomer and thechemical compound into a stream of chemical reactants to facilitate thereacting, wherein the chemical reactants comprise the intermediatepolymer, the chemical base, and the organocatalyst.
 9. A systemcomprising: a flow reactor that houses a stream of chemical reactants tofacilitate a polymerization; a memory that stores computer executablecomponents; and a processor, operably coupled to the memory, and thatexecutes the computer executable components stored in the memory,wherein the computer executable components comprise: an analysiscomponent, operatively coupled to the processor, that controls aparameter of the flow reactor based on a characteristic of a homopolymerproduced by the polymerization, wherein the chemical reactants comprisea cyclic monomer and an organocatalyst comprising a thiourea anion,wherein the polymerization is a ring-opening polymerization having aresidence time within the flow reactor of greater than or equal to 0.006seconds and less than or equal to 3.5 seconds.
 10. The system of claim9, wherein the cyclic monomer is selected from a group consisting of alactone monomer, a cyclic carbonate monomer, a substituted cycliccarbonate monomer, a cyclic phospholane monomer, a morpholinone monomer,tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone,and 2-thiepanone.
 11. The system of claim 9, wherein the flow reactorcomprises a sensor that detects the characteristic, wherein theparameter affects a polymerization condition of the polymerization. 12.The system of claim 11, wherein the polymerization condition is selectedfrom a group consisting of a flow rate of the stream, a turbulence ofthe stream within the flow reactor, and an amount of chemical reactantscomprised within the stream.
 13. The system of claim 9, wherein theanalysis component controls the parameter via cloud computingenvironment.
 14. A method, comprising: forming a polyester homopolymerby a ring-opening polymerization of a cyclic monomer in the presence ofan organocatalyst comprising a thiourea anion, wherein the ring-openingpolymerization is performed at a residence time within a flow reactor ofgreater than or equal to 0.006 seconds and less than or equal to 3.5seconds.
 15. The method of claim 14, wherein the cyclic monomer is alactone monomer.
 16. A method, comprising: forming a polycarbonatehomopolymer by a ring-opening polymerization of a cyclic monomer in thepresence of an organocatalyst comprising thiourea anion, wherein thering-opening polymerization is performed at a residence time within aflow reactor of greater than or equal to 0.006 seconds and less than orequal to 3.5 seconds.
 17. The method of claim 16, wherein the cyclicmonomer is a cyclic carbonate monomer.